Compositions Comprising Multi-valent Cations and Phosphono-phosphate Containing Polymers

ABSTRACT

Disclosed are novel phosphono-phosphate polymer compositions with multi-valent cations in aqueous solutions. These compositions can further include mono or multivalent anions.

TECHNICAL FIELD OF THE INVENTION

The present invention relates to compositions of novelphosphono-phosphate containing polymers with multivalent metal cationsin aqueous solutions. The present invention further relates to novelphosphono-phosphate containing polymers with multivalent metal cationsand additional mono-valent or multi-valent anions in aqueous solutions.

BACKGROUND OF THE INVENTION

Chemical structures and polymers that interact with multivalent cationsin aqueous solution are useful for manipulation of these systems. Inparticular structures and polymers able to interact with multivalentcations in a manner that prevents the multivalent cations fromprecipitating from the aqueous solution has multiple uses.Polyphosphates and pyrophosphate, for example, have been used asbuilders in laundry and dish formulations to control calcium and indrilling muds to prevent precipitation. They have also been used in theoral care industry to help control tartar and reduce the thickness ofthe pellicle layer on teeth resulting in a slick tooth feel. Similarly,bisphosphonates, and hydroxy-bisphosphonates are active components inosteoporosis pharmaceuticals due to their strong interaction withcalcium hydroxy apatite surfaces and are also used as crystal growthinhibitors in dishwashing liquids and boiler systems. Each of theseexamples suffer from an inherent limitation. Polyphosphates are prone todegradation over time in aqueous solutions at all pH's, ultimatelyleading to an increase in ortho phosphate in solution. Polyphosphatesare, however, generally safe for consumption and find use in differentfood products. Bisphosphonates and hydroxy-bisphosphonates are,conversely, stable in water for long periods of time, and can, dependingupon the nature of the organic group attached to the bisphosphonatecarbon, be made quite soluble in organic systems. Bisphosphonates,however, are bone active and hence cannot be used in foods or othersystems where they might be accidently consumed due to their potentpharmacology. Polymers containing bisphosphonates of sufficientmolecular weight to not pass through the intestinal wall would likelynot be bone active, however any low molecular weight residual monomersor oligomers that could pass through the intestinal wall make the use ofsuch polymers prohibitive in potential consumable contexts. In addition,since bisphosphonates do not break down readily, their activity canpersist in the environment after use.

Therefore, a need still exists for a phosphate composition that is ableto interact with and prevent precipitation of multivalent cations in andfrom aqueous solution, while not easily degrading and remaining safe forhuman consumption.

SUMMARY OF THE INVENTION

It has surprisingly been found that the phosphono-phosphate chemicalgroup ameliorates the concerns of polyphosphates and bisphosphonateswhile finding utility in similar aqueous compositions. In particular,compositions that contain a phosphono-phosphate group, monomers thatcontain a phosphono-phosphate group, and polymers that contain aphosphono-phosphate group, whether by incorporation of a monomercontaining a phosphono-phosphate group, or by post polymerizationmodification to add a phosphono-phosphate group, can be used to preventmultivalent cations from precipitating from solution.Phosphono-phosphate containing structures can also be used inapplications where polyphosphates and bisphosphonate use is limited. Thephosphono-phosphate group is conditionally stable and will only releasephosphate under acidic or catalyzed conditions. Hence thephosphono-phosphate group is more stable than polyphosphate, but not asstable as bisphosphonates. This enables formulation into systems wherenon-detrimental effects of consumption and water stability are a must.

In one embodiment, the present invention is directed to an aqueouscomposition comprising a metal salt comprising one or more multivalentcations and a polymer having the structure of Formula 1:

wherein:

-   -   ε is the site of attachment to a carbon atom in the polymer        backbone, side group, or side chain;    -   R₁ is selected from the group consisting of —H, metal salt        having Na, K, or L₁ cation, amine cation salt, and a structure        of Formula 2:

-   -   -   wherein:        -   θ is the site of attachment to Formula 1,        -   R₄ and R₅ are independently selected from the group            consisting of —H, metal salt having Na, K, or L₁ cation, and            amine cation salt;

    -   R₂ is selected from the group consisting of —H, metal salt        having Na, K, or L₁ cation, amine cation salt, and a structure        of Formula 3:

-   -   -   wherein:        -   θ is the site of attachment to Formula 1,        -   R₆, and R₇ are independently selected from the group            consisting of —H, metal salt having Na, K, or L₁ cation, and            amine cation salt, and        -   n is an integer from 1 to 22; and

    -   R₃ is selected from the group consisting of —H, metal salt        having Na, K, or L₁ cation, and amine cation salt.

In one embodiment of the composition, the multivalent metal cations areselected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn, Fe,and Al.

In one embodiment of the composition, the aqueous composition furthercomprises an anion selected from the group consisting of F⁻, Cl⁻, Br⁻,I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄ ⁻³, HPO₄ ⁻², H₂PO₄ ⁻, SO₄ ⁻², HSO₄ ⁻,PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇ ⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹).

In one embodiment of the composition, the aqueous composition furthercomprises an additional metal salt having a monovalent cation.

In one embodiment of the composition, the multivalent metal cations areselected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn, Fe,and Al, and the aqueous composition further comprises an anion selectedfrom the group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻,PO₄ ⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴,HP₂O₇ ⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹).

In one embodiment of the composition, the multivalent metal cations areselected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn, Fe,and Al, and the aqueous composition further comprises an anion selectedfrom the group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻,PO₄ ⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴,HP₂O₇ ⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹) and further comprises anadditional metal salt having a monovalent cation.

In one embodiment of the composition, said polymer further comprises arepeat unit with a structure of Formula 4:

-   -   wherein:        -   ω is the site of attachment to the phosphono-phosphate group            of Formula 1;        -   ψ are the sites of attachment to other repeat units in the            polymer backbone;        -   R₈ is selected from the group consisting of —H and —CH₃;        -   L₁ is selected from the group consisting of a chemical bond,            arenediyl, and a structure of Formula 4:

-   -   wherein:        -   α is the site of attachment to the polymer backbone;        -   β is the site of attachment to the phosphono-phosphate group            of Formula 1;        -   X is selected from the group consisting of the structures in            Formulas 6-12;

-   -   -   wherein:        -   R₉ is selected from the group consisting of —H,            alkyl_((C1-8)), phosphonoalkyl, and            phosphono(phosphate)alkyl; and

    -   Y is selected from the group consisting of alkanediyl,        alkoxydiyl, alkylaminodiyl and alkenediyl.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4, and the multivalent metal cationsare selected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn,Fe, and Al.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4, and the aqueous composition furthercomprises an anion selected from the group consisting of F⁻, Cl⁻, Br⁻,I⁻, OH⁻ S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄ ⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻,PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇ ⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻⁴, and (PO₃ ⁻¹).

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4, and the aqueous composition furthercomprises an additional metal salt having a monovalent cation.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4, the multivalent metal cations areselected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn, Fe,and Al, and the aqueous composition further comprises an anion selectedfrom the group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻,PO₄ ⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴,HP₂O₇ ⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹ and (PO₃ ⁻¹).

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4, the multivalent metal cations areselected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn, Fe,and Al, the aqueous composition further comprises an anion selected fromthe group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹) and the aqueous compositionfurther comprises an additional metal salt having a monovalent cation.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4 and said polymer further comprises arepeat unit with a structure different than Formula 4.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a GPC trace plot resulting from polymer analysis.

FIG. 2 is a GPC trace plot resulting from polymer analysis.

DETAILED DESCRIPTION OF THE INVENTION

While the specification concludes with claims particularly pointing anddistinctly claiming the invention, it is believed the present inventionwill be better understood from the following description.

All percentages herein are by moles of the compositions unless otherwiseindicated.

All ratios are molar ratios unless otherwise indicated.

All percentages, ratios, and levels of ingredients referred to hereinare based on the actual amount of the ingredient by moles, and do notinclude solvents, fillers, or other materials with which the ingredientmay be combined as commercially available products, unless otherwiseindicated.

As used herein, “comprising” means that other steps and otheringredients which do not affect the end result can be added. This termencompasses the terms “consisting of” and “consisting essentially of”.

All cited references are incorporated herein by reference in theirentireties. Citation of any reference is not an admission regarding anydetermination as to its availability as prior art to the claimedinvention.

Definitions

The terms “site” or “site of attachment” or “point of attachment” allmean an atom having an open valence within a chemical group or definedstructural entity that is designated with a symbol such as a simple dash(-) or a lower case letter from the Greek alphabet followed by a dash ora line (e.g. α-, β-, etc.) to indicate that the so-designated atomconnects to another atom in a separate chemical group via a chemicalbond. The symbol “

” when drawn perpendicular across a bond

also indicates a point of attachment of a chemical group. It is notedthat the point of attachment is typically only identified in this mannerfor larger chemical groups in order to unambiguously assist the readerin identifying the point of attachment to the atom from which the bondextends. A site or point of attachment on a first chemical group ordefined structural entity connects to a site or point of attachment on asecond chemical group or defined structural entity via either single,double, or triple covalent bonds in order to satisfy the normal valencyof the atoms connected.

The term “radical” indicates any connected group of atoms, such as amethyl group, a carboxyl group, or a phosphono-phosphate group that ispart of a larger molecule.

When used in the context of a chemical group: “hydrogen” means —H;“hydroxy” means —OH; “oxo” means ═O; “carbonyl” means —C(═O)—; “carboxy”and “carboxylate” mean —C(═O)OH (also written as —COOH or —CO2H) or adeprotonated form thereof; “amino” means —NH2; “hydroxyamino” means—NHOH; “nitro” means —NO2; “imino” means ═NH; “amine oxide” means N⁺O⁻where N has three covalent bonds to atoms other than O; “hydroxamic” or“hydroxamate” means —C(O)NHOH or a deprotonated form thereof; in amonovalent context “phosphate” means —OP(O)(OH)₂ or a deprotonated formthereof; in a divalent context “phosphate” means —OP(O)(OH)O— or adeprotonated form thereof; “phosphonate” means C—P(O)(OH)₂ or adeprotonated form thereof, where the C has a normal valence of four andthree covalent bonds to atoms other than P; “phosphono-phosphate” meansa phosphonate that is chemically bound through a shared oxygen atom toat least one phosphate such as but not limited tophosphono-monophosphate C—P(O)(OH)OP(O)(OH)₂, phosphono-diphosphateC—P(O)(OP(O)(OH)₂)OP(O)(OH)₂, phosphono-cyclodiphosphate

phosphono-polyphosphate C—P(O)(OH)OP(O)(OH)OP(O)(OH)₂, andphosphono-polyphosphate C—P(O)(OH)(OP(O)(OH))_(n)OP(O)(OH)₂, where n isan integer between 1 and 100, or a deprotonated form thereof, where theC has a normal valence of four and three covalent bonds to atoms otherthan P; “phosphinate” means C—P(O)(OH)(C) or a deprotonated formthereof, where both C have a normal valence of four and three additionalbonds to atoms other than P; “sulfate” means —OS(O)₂OH or deprotonatedform thereof; “sulfonate” means CS(O)₂OH or a deprotonated form thereofwhere the C has a normal valence of four and three additional bonds toatoms other than S; “sulfinate” means CS(O)OH or a deprotonated formthereof, where the C has a normal valence of four and three additionalbonds to atoms other than S; “mercapto” means —SH; “thio” means ═S;“sulfonyl” means —S(O)2-; and “sulfinyl” means —S(O)—.

For the chemical groups and classes below, the following parentheticalsubscripts further define the chemical group/class as follows: “(Cn)”defines the exact number (n) of carbon atoms in the chemicalgroup/class. “(C≤n)” defines the maximum number (n) of carbon atoms thatcan be in the chemical group/class, with the minimum number as small aspossible for the chemical group in question, e.g., it is understood thatthe minimum number of carbon atoms in the chemical group“alkenyl_((C≤8))” or the chemical class “alkene_((C≤8))” is two. Forexample, “alkoxy_((C≤8))” designates those alkoxy groups having from 1to 8 carbon atoms. (Cn-n′) defines both the minimum (n) and maximumnumber (n′) of carbon atoms in the chemical group. Similarly,alkyl_((C2-8)) designates those alkyl groups having from 2 to 8 carbonatoms, inclusive.

The term “cation” refers to an atom, molecule, or a chemical group witha net positive charge including single and multiply charged species.Cations can be individual atoms such as metals, non-limiting examplesinclude Na⁺ or Ca⁺², individual molecules, non-limiting examples include(CH₃)₄N⁺, or a chemical group, non-limiting examples include-N(CH₃)₃ ⁺.The term “amine cation” refers to a particular molecular cation, of theform NR₄ ⁺ where the four substituting R moieties can be independentlyselected from H and alkyl, non-limiting examples include NH₄ ⁺(ammonium), CH₃NH—₃ ⁺ (methylammonium), CH₃CH₂NH₃ ⁺ (ethylammonium),(CH₃)₂NH₂ ⁺ (dimethylammonium), (CH₃)₃NH⁺ (trimethylammonium), and(CH₃)₄N⁺ (tetramethylammonium).

The term “anion” refers to an atom, molecule, or chemical group with anet negative charge including single and multiply charged species.Anions can be individual atoms, for example but not limited to halidesF⁻, Cl⁻, Br⁻, individual molecules, non-limiting examples include CO₃⁻², H₂PO₄ ⁻, HPO₄ ⁻², PO₄ ⁻³, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴,HP₂O₇ ⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹), or a chemical group,non-limiting examples include sulfate, phosphate, sulfonate,phosphonate, phosphinate, sulfonate, monofluorophosphate, pyrophosphate,polyphosphate, mercapto, carboxylate, amine oxide, hydroxamate andhydroxyl amino. Deprotonated forms of previously defined chemical groupsare considered anionic groups if the removal of the proton results in anet negative charge. In solutions, chemical groups are capable of losinga proton and become anionic as a function of pH according to theHenderson-Hasselbach equation (pH=pKa+log₁₀([A⁻]/[HA]; where [HA] is themolar concentration of an undissociated acid and [A⁻] is the molarconcentration of this acid's conjugate base). When the pH of thesolution equals the pKa value of functional group, 50% of the functionalgroup will be anionic, while the remaining 50% will have a proton.Typically, a functional group in solution can be considered anionic ifthe pH is at or above the pKa of the functional group.

Polyphosphate is a multivalent anion consisting of dehydrated phosphategroups. Each phosphate repeat unit that is not in a terminal position ismonovalent. Each phosphate in a terminal position is divalent. The totalmultivalent charge of a molecule of polyphosphate then depends upon howmany repeat units are present in the molecule. Commercial polyphosphatesare mixtures of molecules with various numbers of repeat units ofphosphate. Typical numbers of repeat units can average from 6 to 30. Theformula weight of polyphosphate can be approximated by ignoring thecontribution from the end groups. For the case of the full sodium formof polyphosphate, this approximation ignores one NaO on one end and oneNa on the other. For 6 repeat units, this approximation underestimatesthe formula weight by about 10%. At 12 repeats, it underestimates about5%, 24 by 2.5% and 30 by 2%. Polyphosphate can be represented by thechemical group (PO₃ ⁻¹). Polyphosphate reacts with water to form shorterchains. For purposes of calculating equivalent charge and molecularweight when using polyphosphate here-in, polyphosphate is assumed to bean infinitely long chain of phosphates with no end groups, and the molarequivalents of phosphate and charge are based on the (PO₃ ⁻¹) group.

The term “salt” or “salts” refers to the charge neutral combination ofone or more anions and cations. For example, when R is denoted as a saltfor the carboxylate group, —COOR, it is understood that the carboxylate(—COO—) is an anion with a negative charge −1, and that the R is acation with a positive charge of +1 to form a charge neutral entity withone anion of charge −1, or R is a cation with a positive charge of +2 toform a charge neutral entity with two anions both of −1 charge.

The term “saturated” as used herein means the chemical compound or groupso modified has no carbon-carbon double and no carbon-carbon triplebonds, except as noted below. In the case of substituted versions ofsaturated chemical groups, one or more carbon oxygen double bond or acarbon nitrogen double bond may be present. When such a bond is present,then carbon-carbon double bonds that may occur as part of keto-enoltautomerism or imine/enamine tautomerism are not precluded.

The term “aliphatic” when used without the “substituted” modifiersignifies that the chemical compound/group so modified is an acyclic orcyclic, but non-aromatic hydrocarbon chemical compound or group. Inaliphatic chemical compounds/groups, the carbon atoms can be joinedtogether in straight chains, branched chains, or non-aromatic rings(alicyclic). Aliphatic chemical compounds/groups can be saturated, thatis joined by single bonds (alkanes/alkyl), or unsaturated, with one ormore double bonds (alkenes/alkenyl), or with one or more triple bonds(alkynes/alkynyl).

The term “alkyl” when used without the “substituted” modifier refers toa monovalent saturated aliphatic group with a carbon atom as the pointof attachment, a linear or branched, cyclo, cyclic, or acyclicstructure, and no atoms other than carbon and hydrogen. Thus, as usedherein cycloalkyl is a subset of alkyl, with the carbon atom that formsthe point of attachment also being a member of one or more non-aromaticring structures wherein the cycloalkyl group consists of no atoms otherthan carbon and hydrogen. As used herein, the term does not preclude thepresence of one or more alkyl groups (carbon number limitationpermitting) attached to the ring or ring system. The groups —CH₃ (Me),—CH₂CH₃ (Et), —CH₂CH₂CH₃ (n-Pr or propyl), —CH(CH₃)₂ (i-Pr, ′Pr, orisopropyl), —CH(CH₂)₂ (cyclopropyl), —CH₂CH₂CH₂CH₃ (n-Bu),—CH(CH₃)CH₂CH₃ (sec-butyl), —CH₂CH(CH₃)₂ (isobutyl), —C(CH₃)₃(tertbutyl, t-butyl, t-Bu, or tBu), —CH₂C(CH₃)₃ (neo-pentyl),cyclobutyl, cyclopentyl, cyclohexyl, and cyclohexylmethyl arenon-limiting examples of alkyl groups. The term “alkanediyl” when usedwithout the “substituted” modifier refers to a divalent saturatedaliphatic group, with one or two saturated carbon atom(s) as thepoint(s) of attachment, a linear or branched, cyclo, cyclic or acyclicstructure, no carbon-carbon double or triple bonds, and no atoms otherthan carbon and hydrogen. The groups, —CH₂— (methylene), —CH₂CH₂—,—CH₂C(CH₃)₂CH₂—, and —CH₂CH₂CH₂— are non-limiting examples of alkanediylgroups. The term “alkylidene” when used without the “substituted”modifier refers to the divalent group ═CRR′ in which R and R′ areindependently hydrogen, alkyl, or R and R′ are taken together torepresent an alkanediyl having at least two carbon atoms. Non-limitingexamples of alkylidene groups include: ═CH₂, ═CH(CH₂CH₃), and ═C(CH₃)₂.An “alkane” refers to the compound H—R, wherein R is alkyl as this termis defined above. When any of these terms is used with the “substituted”modifier one or more hydrogen atom has been independently replaced by—OH, —F⁻, —Cl, —Br⁻, —I, —NH₂, —NO₂, —CO₂H, —CO₂CH₃, —CN, —SH, —OCH₃,—OCH₂CH₃, —C(O)CH₃, —NHCH₃, —NHCH₂CH₃, —N(CH₃)₂, —C(O)NH₂, —OC(O)CH₃,—S(O)₂NH₂, —P(O)(OH)₂, —P(O)(OH)OP(O)(OH)₂, —OP(O)(OH)₂,—OP(O)(OH)OP(O)(OH)₂, —S(O)₂(OH), or —OS(O)₂(OH). The following groupsare non-limiting examples of substituted alkyl groups: —CH₂OH, —CH₂Cl,—CF₃, —CH₂CN, —CH₂C(O)OH, —CH₂C(O)OCH₃, —CH₂C(O)NH₂, —CH₂C(O)CH₃,—CH₂OCH₃, —CH₂OC(O)CH₃, —CH₂NH₂, —CH₂N(CH₃)₂, —CH₂CH₂Cl, —CH₂P(O)(OH)₂,—CH₂P(O)(OH)OP(O)(OH)₂, —CH₂S(O)₂(OH), and —CH₂OS(O)₂(OH). The term“haloalkyl” is a subset of substituted alkyl, in which one or morehydrogen atoms has been substituted with a halo group and no other atomsaside from carbon, hydrogen and halogen are present. The group, —CH₂Clis a non-limiting example of a haloalkyl. The term “fluoroalkyl” is asubset of substituted alkyl, in which one or more hydrogen has beensubstituted with a fluoro group and no other atoms aside from carbon,hydrogen and fluorine are present. The groups, —CH₂F⁻, —CF₃, and —CH₂CF₃are non-limiting examples of fluoroalkyl groups. The term“phosphonoalkyl” is a subset of substituted alkyl, in which one or moreof the hydrogen has been substituted with a phosphonate group and noother atoms aside from carbon, hydrogen, phosphorous, and oxygen arepresent. The groups, —CH₂P(O)(OH)₂, and —CH₂CH₂P(O)(OH)₂, and thecorresponding deprotonated forms thereof, are non-limiting examples of aphosphonoalkyl.

The term “phosphono(phosphate)alkyl” is a subset of substituted alkyl,in which one or more of the hydrogen has been substituted with aphosphono-phosphate group and no other atoms aside from carbon,hydrogen, phosphorous, and oxygen are present. The groups,—CH₂P(O)(OH)OP(O)(OH)₂, and —CH₂CH₂P(O)(OH)OP(O)(OH)₂, and correspondingdeprotonated forms thereof, are non-limiting examples of phospho no(phosphate)alkyl.

The term “sulfonoalkyl” is a subset of substituted alkyl, in which oneor more of the hydrogen has been substituted with a sulfonate group andno other atoms aside from carbon, hydrogen, sulfur, and oxygen arepresent. The groups, —CH₂S(O)₂OH and —CH₂CH₂S(O)₂OH, and thecorresponding deprotonated forms thereof, are non-limiting examples of asulfonoalkyl.

The term “alkenyl” when used without the “substituted” modifier refersto a monovalent unsaturated aliphatic group with a carbon atom as thepoint of attachment, a linear or branched, cyclo, cyclic or acyclicstructure, at least one nonaromatic carbon-carbon double bond, nocarbon-carbon triple bonds, and no atoms other than carbon and hydrogen.Non-limiting examples of alkenyl groups include: —CH═CH₂ (vinyl),—C(CH₃)═CH₂ (methyl-vinyl), —CH═CHCH₃, —CH═CHCH₂CH₃, —CH₂CH═CH₂ (allyl),—CH₂CH═CHCH₃, and —CH═CHCH═CH₂. The term “alkenediyl” when used withoutthe “substituted” modifier refers to a divalent unsaturated aliphaticgroup, with two carbon atoms as points of attachment, a linear orbranched, cyclo, cyclic or acyclic structure, at least one nonaromaticcarbon-carbon double bond, no carbon-carbon triple bonds, and no atomsother than carbon and hydrogen. The groups, >C═CH₂ (vinylidine),—CH═CH—, —CH═C(CH₃)CH₂—, and —CH═CHCH₂—, are non-limiting examples ofalkenediyl groups. It is noted that while the alkenediyl group isaliphatic, once connected at both ends, this group is not precluded fromforming part of an aromatic structure. The terms “alkene” or “olefin”are synonymous and refer to a compound having the formula H—R, wherein Ris alkenyl as this term is defined above. A “terminal alkene” refers toan alkene having just one carbon-carbon double bond, wherein that bondforms a vinyl group at one end of the molecule. When any of these termsare used with the “substituted” modifier one or more hydrogen atom hasbeen independently replaced by —OH, —F, —Cl, —Br, —I, —NH, —NO₂, —CO₂H,—CO₂CH₃, —CN, —SH, —OCH₃, —OCH₂CH₃, —C(O)CH₃, —NHCH₃, —NHCH₂CH₃,—N(CH₃)₂, —C(O)NH₂, —OC(O)CH₃, or —S(O)₂NH₂. The groups, —CH═CHF,—CH═CHCl and —CH═CHBr, are non-limiting examples of substituted alkenylgroups.

The term “alkynyl” when used without the “substituted” modifier refersto a monovalent unsaturated aliphatic group with a carbon atom as thepoint of attachment, a linear or branched, cyclo, cyclic or acyclicstructure, at least one carbon-carbon triple bond, and no atoms otherthan carbon and hydrogen. As used herein, the term alkynyl does notpreclude the presence of one or more non-aromatic carbon-carbon doublebonds. The groups, —C≡CH, —C≡CCH₃, and —CH₂C≡CCH₃, are non-limitingexamples of alkynyl groups. An “alkyne” refers to the compound H—R,wherein R is alkynyl. When any of these terms are used with the“substituted” modifier one or more hydrogen atom has been independentlyreplaced by —OH, —F, —Cl, —Br, —I, —NH₂, —NO₂, —CO₂H, —CO₂CH₃, —CN, —SH,—OCH₃, —OCH₂CH₃, —C(O)CH₃, —NHCH₃, —NHCH₂CH₃, —N(CH₃)₂, —C(O)NH₂,—OC(O)CH₃, or —S(O)₂NH₂.

The term “aryl” when used without the “substituted” modifier refers to amonovalent unsaturated aromatic group with an aromatic carbon atom asthe point of attachment, said carbon atom forming part of a one or moresix membered aromatic ring structure, wherein the ring atoms are allcarbon, and wherein the group consists of no atoms other than carbon andhydrogen. If more than one ring is present, the rings may be fused orunfused. As used herein, the term does not preclude the presence of oneor more alkyl or aralkyl groups (carbon number limitation permitting)attached to the first aromatic ring or any additional aromatic ringpresent. Non-limiting examples of aryl groups include phenyl (—Ph),methylphenyl, (dimethyl)phenyl, —C₆H₄CH₂CH₃ (ethylphenyl), naphthyl, anda monovalent group derived from biphenyl. The term “arenediyl” when usedwithout the “substituted” modifier refers to a divalent aromatic groupwith two aromatic carbon atoms as points of attachment, said carbonatoms forming part of one or more six-membered aromatic ringstructure(s) wherein the ring atoms are all carbon, and wherein themonovalent group consists of no atoms other than carbon and hydrogen. Asused herein, the term does not preclude the presence of one or morealkyl, aryl or aralkyl groups (carbon number limitation permitting)attached to the first aromatic ring or any additional aromatic ringpresent. If more than one ring is present, the rings may be fused orunfused. Unfused rings may be connected via one or more of thefollowing: a covalent bond, alkanediyl, or alkenediyl groups (carbonnumber limitation permitting). Non-limiting examples of arenediyl groupsinclude:

An “arene” refers to the compound H—R, wherein R is aryl as that term isdefined above. Benzene and toluene are non-limiting examples of arenes.When any of these terms are used with the “substituted” modifier one ormore hydrogen atom has been independently replaced by —OH, —F, —Cl, —Br,—I, —NH₂, —NO₂, —CO₂H, —CO₂CH₃, —CN, —SH, —OCH₃, —OCH₂CH₃, —C(O)CH₃,—NHCH₃, —NHCH₂CH₃, —N(CH₃)₂, —C(O)NH₂, —OC(O)CH₃, or —S(O)₂NH₂.

The term “acyl” when used without the “substituted” modifier refers tothe group —C(O)R, in which R is a hydrogen, alkyl, aryl, aralkyl orheteroaryl, as those terms are defined above. The groups, —CHO (formyl),—C(O)CH₃ (acetyl, Ac), —C(O)CH₂CH₃, —C(O)CH₂CH₂CH₃, —C(O)CH(CH₃)₂,—C(O)CH(CH₂)₂, —C(O)C₆H₅, —C(O)C₆H₄CH₃, —C(O)CH₂C₆H₅, —C(O)(imidazolyl)are non-limiting examples of acyl groups. A “thioacyl” is defined in ananalogous manner, except that the oxygen atom of the group —C(O)R hasbeen replaced with a sulfur atom, —C(S)R. The term “aldehyde”corresponds to an alkane, as defined above, wherein at least one of thehydrogen atoms has been replaced with a —CHO group. When any of theseterms are used with the “substituted” modifier one or more hydrogen atom(including a hydrogen atom directly attached the carbonyl orthiocarbonyl group, if any) has been independently replaced by —OH, —F,—Cl, —Br, —I, —NH2, —NO₂, —CO₂H, —CO₂CH₃, —CN, —SH, —OCH₃, —OCH₂CH₃,—C(O)CH₃, —NHCH₃, —NHCH₂CH₃, —N(CH₃)₂, —C(O)NH₂, —OC(O)CH₃, or—S(O)₂NH₂. The groups, —C(O)CH₂CF₃, —CO₂H (carboxyl), —CO₂CH₃(methylcarboxyl), —CO₂CH₂CH₃, —C(O)NH₂ (carbamoyl), and —CON(CH₃)₂, arenon-limiting examples of substituted acyl groups. The term “alkoxy” whenused without the “substituted” modifier refers to the group —OR, inwhich R is an alkyl, as that term is defined above. Non-limitingexamples of alkoxy groups include: —OCH₃ (methoxy), —OCH₂CH₃ (ethoxy),—OCH₂CH₂CH₃, —OCH(CH₃)₂ (isopropoxy), —O(CH₃)₃ (tert-butoxy),—OCH(CH₂)₂, —O-cyclopentyl, and —O-cyclohexyl. The terms “alkenyloxy”,“alkynyloxy”, “aryloxy”, “aralkoxy”, “heteroaryloxy”,“heterocycloalkoxy”, and “acyloxy”, when used without the “substituted”modifier, refers to groups, defined as —OR, in which R is alkenyl,alkynyl, aryl, aralkyl, heteroaryl, heterocycloalkyl, and acyl,respectively. The term “alkoxydiyl” refers to the divalent group—O-alkanediyl-, —O-alkanediyl-O—, or -alkanediyl-O-alkanediyl-. The term“alkanediyl-alkoxy” refers to -alkanediyl-O-alkyl. A nonlimiting exampleof alkanedyl-alkoxy is —CH₂—CH₂—O—CH₂—CH₃. The term “alkylthio” and“acylthio” when used without the “substituted” modifier refers to thegroup —SR, in which R is an alkyl and acyl, respectively. The term“alcohol” corresponds to an alkane, as defined above, wherein at leastone of the hydrogen atoms has been replaced with a hydroxy group. Theterm “ether” corresponds to an alkane, as defined above, wherein atleast one of the hydrogen atoms has been replaced with an alkoxy group.When any of these terms is used with the “substituted” modifier one ormore hydrogen atom has been independently replaced by —OH, —F⁻, —Cl,—Br⁻, —I, —NH₂, —NO₂, —CO₂H, —CO₂CH₃, —CN, —SH, —OCH₃, —OCH₂CH₃,—C(O)CH₃, —NHCH₃, —NHCH₂CH₃, —N(CH₃)₂, —C(O)NH₂, —OC(O)CH₃, or—S(O)₂NH₂.

The term “alkylamino” when used without the “substituted” modifierrefers to the group —NHR, in which R is an alkyl, as that term isdefined above. Non-limiting examples of alkylamino groups include:—NHCH₃ and —NHCH₂CH₃. The term “dialkylamino” when used without the“substituted” modifier refers to the group —NRR′, in which R and R′ canbe the same or different alkyl groups, or R and R′ can be taken togetherto represent an alkanediyl. Non-limiting examples of dialkylamino groupsinclude: —N(CH₃)₂, —N(CH₃)(CH₂CH₃), and N-pyrrolidinyl. The terms“alkoxyamino”, “alkenylamino”, “alkynylamino”, “arylamino”,“aralkylamino”, “heteroarylamino”, “heterocycloalkylamino” and“alkylsulfonylamino” when used without the “substituted” modifier,refers to groups, defined as —NHR, in which R is alkoxy, alkenyl,alkynyl, aryl, aralkyl, heteroaryl, heterocycloalkyl, and alkylsulfonyl,respectively. A non-limiting example of an arylamino group is —NHC₆H₅.The term “amido” (acylamino), when used without the “substituted”modifier, refers to the group —NHR, in which R is acyl, as that term isdefined above. A non-limiting example of an amido group is —NHC(O)CH₃.The term “alkylimino” when used without the “substituted” modifierrefers to the divalent group ═NR, in which R is an alkyl, as that termis defined above. The term “alkylaminodiyl” refers to the divalent group—NH-alkanediyl-, —NH-alkanediyl-NH—, or -alkanediyl-NH-alkanediyl-. Whenany of these terms is used with the “substituted” modifier one or morehydrogen atom has been independently replaced by —OH, —F, —Cl, —Br, —I,—NH₂, —NO₂, —CO₂H, —CO₂CH₃, —CN, —SH, —OCH₃, —OCH₂CH₃, —C(O)CH₃, —NHCH₃,—NHCH₂CH₃, —N(CH₃)₂, —C(O)NH₂, —OC(O)CH₃, or —S(O)₂NH₂. The groups—NHC(O)OCH₃ and —NHC(O)NHCH₃ are non-limiting examples of substitutedamido groups.

The terms “alkylsulfonyl” and “alkylsulfinyl” when used without the“substituted” modifier refers to the groups —S(O)₂R and —S(O)R,respectively, in which R is an alkyl, as that term is defined above. Theterms “alkenylsulfonyl”, “alkynylsulfonyl”, “arylsulfonyl”,“aralkylsulfonyl”, “heteroarylsulfonyl”, and “heterocycloalkylsulfonyl”are defined in an analogous manner. When any of these terms is used withthe “substituted” modifier one or more hydrogen atom has beenindependently replaced by —OH, —F, —Cl, —Br, —I, —NH₂, —NO₂, —CO₂H,—CO₂CH₃, —CN, —SH, —OCH₃, —OCH₂CH₃, —C(O)CH₃, —NHCH₃, —NHCH₂CH₃,—N(CH₃)₂, —C(O)NH₂, —OC(O)CH₃, or —S(O)₂NH₂.

The term “alkylphosphate” when used without the “substituted” modifierrefers to the group —OP(O)(OH)(OR) or a deprotonated form thereof, inwhich R is an alkyl, as that term is defined above. Nonlimiting examplesof alkylphosphate groups include: —OP(O)(OH)(OMe) and —OP(O)(OH)(OEt).The term “dialkylphosphate” when used without the “substituted” modifierrefers to the group —OP(O)(OR)(OR′), in which R and R′ can be the sameor different alkyl groups, or R and R′ can be taken together torepresent an alkanediyl. Non-limiting examples of dialkylphosphategroups include: —OP(O)(OMe)₂, —OP(O)(OEt)(OMe) and —OP(O)(OEt)₂. Whenany of these terms is used with the “substituted” modifier one or morehydrogen atom has been independently replaced by —OH, —F, —Cl, —Br, —I,—NH₂, —NO₂, —CO₂H, —CO₂CH₃, —CN, —SH, —OCH₃, —OCH₂CH₃, —C(O)CH₃, —NHCH₃,—NHCH₂CH₃, —N(CH₃)₂, —C(O)NH₂, —OC(O)CH₃, or —S(O)₂NH₂.

Linking group means either a covalent bond between two other definedgroups, or a series of covalently bound atoms that connect two otherdefined groups wherein the series of covalently bound atoms have no openvalences other than the sites of attachment to the two other definedgroups. Non-limiting examples of a linking group include a covalentbond, alkanediyl, alkenediyl, arenediyl, alkoxydiyl, and alkylaminodiyl.

As used herein, a “chiral auxiliary” refers to a removable chiral groupthat is capable of influencing the stereoselectivity of a reaction.Persons of skill in the art are familiar with such compounds, and manyare commercially available.

Other abbreviations used herein are as follows: DMSO, dimethylsulfoxide; DMF, dimethylformamide; MeCN, acetonitrile; MeOH, methanol;EtOH, ethanol; EtOAc, ethyl acetate; tBuOK, tert-butanol; iPrOH,isopropanol; cHexOH, cyclohexanol; Ac₂O, acetic anhydride; AcOOH,peracetic acid; HCO₂Et, ethyl formate; THF, tetrahydrofuran; MTBE,methyl tert-butyl ether; DME, dimethoxyethane; NBS, N-bromo succinimide;CDI, carbonyldiimidazole; DIEA, diisopropylethylamine; TEA,triethylamine; DMAP, dimethylaminopyridine; NaOH, sodium hydroxide;AAPH, 2,2′-azobis(2-methylpropionamidine)dihydrochloride; CTA,1-Octanethiol; APS, ammonium persulfate; TMP, trimethyl phosphate; VPA,vinyl phosphonic acid; VPP, vinyl phosphono-monophosphate; VPPP, vinylphosphono-pyrophosphate MVPP, methyl-vinyl phosphono-monophosphate; SVS,sodium vinyl sulfonate; AMPS, sodium 2-acrylamido-2-methyl propanesulfonic acid; SPA, 3-sulfopropyl acrylate potassium salt; 22A2MPA2HCl,2,2′-azobis (2-methylpropionamidine)dihydrochloride; VBPP,(4-vinylbenzyl)monophosphono-phosphate; VSME, vinyl sulfonate methylester; NaOMe, sodium methoxide; NaCl, sodium chloride; DMVP, dimethylvinyl phosphonate, MFP, Monofluoro Phosphate.

A “monomer molecule” is defined by the International Union of Pure andApplied Chemistry (IUPAC) as “A molecule which can undergopolymerization thereby contributing constitutional units to theessential structure of a macromolecule.” A polymer is a macromolecule.

A “polymer backbone” or “main chain” is defined by IUPAC as “That linearchain to which all other chains, long or short, or both may be regardedas being pendant” with the note that “Where two or more chains couldequally be considered to be the main chain, that one is selected whichleads the simplest representation of the molecule.” Backbones can be ofdifferent chemical compositions depending upon the starting materialsfrom which they are made. Common backbones from chemically andbiologically synthesized polymers include alkanes, typically from vinylor methyl vinyl polymerizations or cationic and anionic polymerizations,poly esters, from condensation polymerizations, poly amides, such aspoly peptides from polymerizations involving amidation reactions, andpoly ethoxylates from epoxide ring opening.

A “pendant group” or “side group” is defined by IUPAC as “An offshoot,neither oligomeric nor polymeric from a chain.” A side group as suchdoes not include a linear repeated unit.

A “polymer side chain” or “pendant chain” is defined by IUPAC as “Anoligomeric or polymeric offshoot from a macromolecular chain” with theadditional notes that “An oligomeric branch may be termed a short chainbranch” and “A polymeric branch may be termed a long chain branch”.

“Post-polymerization modification” is defined as any reaction ortreatment of a polymer that takes place following polymerization.Post-polymerization modifications include reactions to chemical groupswithin or attached to the polymer backbone, pendant group, or polymerside chains.

The use of the word “a” or “an,” when used in conjunction with the term“comprising” in the claims and/or the specification may mean “one,” butit is also consistent with the meaning of “one or more,” “at least one,”and “one or more than one.”

Throughout this application, the term “about” is used to indicate that avalue includes the inherent variation of error for the device, themethod being employed to determine the value, or the variation thatexists among the study subjects.

The terms “comprise,” “have” and “include” are open ended linking verbs.Any forms or tenses of one or more of these verbs, such as “comprises,”“comprising,” “has,” “having,” “includes” and “including,” are alsoopen-ended. For example, any method that “comprises,” “has” or“includes” one or more steps is not limited to possessing only those oneor more steps and also covers other unlisted steps.

The above definitions supersede any conflicting definition in anyreference that is incorporated by reference herein. The fact thatcertain terms are defined, however, should not be considered asindicative that any term that is undefined is indefinite. Rather, allterms used are believed to describe the invention in terms such that oneof ordinary skill can appreciate the scope and practice the presentinvention.

Compositions of Multi-Valent Cations and Phosphono-Phosphate ContainingPolymers

In one embodiment, the present invention is directed to an aqueouscomposition comprising a metal salt comprising one or more multivalentcations and a polymer having the structure of Formula 1:

wherein:

-   -   ε is the site of attachment to a carbon atom in the polymer        backbone, side group, or sidechain;    -   R₁ is selected from the group consisting of —H, metal salt        having Na, K, or L₁ cation, amine cation salt, and a structure        of Formula 2:

-   -   -   wherein:        -   θ is the site of attachment to Formula 1,        -   R₄ and R₅ are independently selected from the group            consisting of —H, metal salt having Na, K, or L₁ cation, and            amine cation salt;

    -   R₂ is selected from the group consisting of —H, metal salt        having Na, K, or L₁ cation, amine cation salt, and a structure        of Formula 3:

-   -   -   wherein:        -   θ is the site of attachment to Formula 1,        -   R₆, and R₇ are independently selected from the group            consisting of —H, metal salt having Na, K, or L₁ cation, and            amine cation salt, and        -   n is an integer from 1 to 22; and

    -   R₃ is selected from the group consisting of —H, metal salt        having Na, K, or L₁ cation, and amine cation salt.

In one embodiment of the composition, the multivalent metal cations areselected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn, Fe,and Al.

In one embodiment of the composition, the aqueous composition furthercomprises an anion selected from the group consisting of F⁻, Cl⁻, Br⁻,I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄ ⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻,PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇ ⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹).In one embodiment of the composition, the aqueous composition furthercomprises an additional metal salt having a monovalent cation.

In one embodiment of the composition, the multivalent metal cations areselected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn, Fe,and Al, and the aqueous composition further comprises an anion selectedfrom the group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻,PO₄ ⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴,HP₂O₇ ⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹).

In one embodiment of the composition, the multivalent metal cations areselected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn, Fe,and Al, and the aqueous composition further comprises an anion selectedfrom the group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻,PO₄ ⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴,HP₂O₇ ⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹) and further comprises anadditional metal salt having a monovalent cation.

In one embodiment of the composition, said polymer further comprises arepeat unit with a structure of Formula 4:

-   -   wherein:        -   ω is the site of attachment to the phosphono-phosphate group            of Formula 1;        -   ψ are the sites of attachment to other repeat units in the            polymer backbone;        -   R₈ is selected from the group consisting of —H and —CH₃;        -   L₁ is selected from the group consisting of a chemical bond,            arenediyl, and a structure of Formula 4:    -   wherein:

-   -   -   α is the site of attachment to the polymer backbone;        -   β is the site of attachment to the phosphono-phosphate group            of Formula 1;        -   X is selected from the group consisting of the structures in            Formulas 6-Formula 6

-   -   -   wherein:        -   R₉ is selected from the group consisting of —H,            alkyl_((C1-8)), phosphonoalkyl, and            phosphono(phosphate)alkyl; and

    -   Y is selected from the group consisting of alkanediyl,        alkoxydiyl, alkylaminodiyl and alkenediyl.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4, and the multivalent metal cationsare selected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn,Fe, and Al.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4, and the aqueous composition furthercomprises an anion selected from the group consisting of F⁻, Cl⁻, Br⁻,I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄ ⁻³, HPO₄ ⁻², SO₄ ⁻², HSO₄ ⁻, PO₃F⁻²,HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇ ⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹).

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4, and the aqueous composition furthercomprises an additional metal salt having a monovalent cation.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4, the multivalent metal cations areselected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn, Fe,and Al, and the aqueous composition further comprises an anion selectedfrom the group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻,PO₄ ⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴,HP₂O₇ ⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹ and (PO₃ ⁻¹).

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4, the multivalent metal cations areselected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn, Fe,and Al, the aqueous composition further comprises an anion selected fromthe group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹) and the aqueous compositionfurther comprises an additional metal salt having a monovalent cation.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4 and said polymer further comprises arepeat unit with a structure different than Formula 4.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4 and R₈ is —H.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4 and R₈ is —CH₃.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4 and L₁ is a chemical bond.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4, R₈ is —H and L₁ is a chemical bond.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4, R₈ is CH₃ and L₁ is a chemical bond.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4 and L₁ has the structure of Formula 5and X has the structure in Formula 6.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4 and L₁ has the structure of Formula 5and X has the structure in Formula 9.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4 and L₁ has the structure of Formula 5and X has the structure in Formula 11.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4, the multivalent metal cations areselected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn, Fe,and Al, and R₈ is —H.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4, the multivalent metal cations areselected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn, Fe,and Al, and R₈ is —CH₃.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4, the multivalent metal cations areselected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn, Fe,and Al, and L₁ is a chemical bond.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4, the multivalent metal cations areselected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn, Fe,and Al, R₈ is —H, and L₁ is a chemical bond.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4, the multivalent metal cations areselected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn, Fe,and Al, R₈ is —CH₃, and L₁ is a chemical bond.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4, the multivalent metal cations areselected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn, Fe,and Al, and L₁ has the structure of Formula 5 and X has the structure inFormula 6.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4, the multivalent metal cations areselected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn, Fe,and Al, and wherein L₁ has the structure of Formula 5 and X has thestructure in Formula 9.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4, the multivalent metal cations areselected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn, Fe,and Al, and wherein L₁ has the structure of Formula 5 and X has thestructure in Formula 11.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4, the multivalent metal cations areselected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn, Fe,and Al, the aqueous composition further comprises an anion selected fromthe group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹), and R₈ is —H.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4, the multivalent metal cations areselected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn, Fe,and Al, the aqueous composition further comprises an anion selected fromthe group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻⁴, and (PO₃ ⁻¹), and R₈ is —CH₃.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4, the multivalent metal cations areselected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn, Fe,and Al, the aqueous composition further comprises an anion selected fromthe group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹), and U is a chemical bond. In oneembodiment of the composition, said polymer comprises a repeat unit witha structure of Formula 4, the multivalent metal cations are selectedfrom the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn, Fe, and Al, theaqueous composition further comprises an anion selected from the groupconsisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄ ⁻³, HPO₄ ⁻²,H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇ ⁻³, H₂P₂O₇ ⁻²,H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹), R₈ is —H, and L₁ is a chemical bond.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4, the multivalent metal cations areselected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn, Fe,and Al, the aqueous composition further comprises an anion selected fromthe group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹), R₈ is —CH₃, and U is a chemicalbond.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4, the multivalent metal cations areselected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn, Fe,and Al, the aqueous composition further comprises an anion selected fromthe group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹), and L₁ has the structure ofFormula 5 and X has the structure in Formula 6.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4, the multivalent metal cations areselected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn, Fe,and Al, the aqueous composition further comprises an anion selected fromthe group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹), and L₁ has the structure ofFormula 5 and X has the structure in Formula 9.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4, the multivalent metal cations areselected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn, Fe,and Al, the aqueous composition further comprises an anion selected fromthe group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇⁻³, H₂P₂O₇ ², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹), and L₁ has the structure ofFormula 5 and X has the structure in Formula 11.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4, the multivalent metal cations areselected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn, Fe,and Al, the aqueous composition further comprises an anion selected fromthe group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹), the aqueous composition furthercomprises an additional metal salt having a monovalent cation and R₈ is—H.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4, the multivalent metal cations areselected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn, Fe,and Al, the aqueous composition further comprises an anion selected fromthe group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹), the aqueous composition furthercomprises an additional metal salt having a monovalent cation and R₈ is—CH₃.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4, the multivalent metal cations areselected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn, Fe,and Al, the aqueous composition further comprises an anion selected fromthe group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹), the aqueous composition furthercomprises an additional metal salt having a monovalent cation and L₁ isa chemical bond.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4, the multivalent metal cations areselected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn, Fe,and Al, the aqueous composition further comprises an anion selected fromthe group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹ and (PO₃ ⁻¹), the aqueous composition furthercomprises an additional metal salt having a monovalent cation, R₈ is —H,and L₁ is a chemical bond.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4, the multivalent metal cations areselected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn, Fe,and Al, the aqueous composition further comprises an anion selected fromthe group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇⁻³, H₂P₂O₇ ², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹), the aqueous composition furthercomprises an additional metal salt having a monovalent cation, R₈ is—CH₃, and L₁ is a chemical bond.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4, the multivalent metal cations areselected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn, Fe,and Al, the aqueous composition further comprises an anion selected fromthe group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹), the aqueous composition furthercomprises an additional metal salt having a monovalent cation and L₁ hasthe structure of Formula 5 and X has the structure in Formula 6.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4, the multivalent metal cations areselected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn, Fe,and Al, the aqueous composition further comprises an anion selected fromthe group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹), the aqueous composition furthercomprises an additional metal salt having a monovalent cation and L₁ hasthe structure of Formula 5 and X has the structure in Formula 9.

In one embodiment of the composition, said polymer comprises a repeatunit with a structure of Formula 4, the multivalent metal cations areselected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn, Fe,and Al, the aqueous composition further comprises an anion selected fromthe group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹), the aqueous composition furthercomprises an additional metal salt having a monovalent cation and L₁ hasthe structure of Formula 5 and X has the structure in Formula 11.

In one embodiment, the present invention is directed to a method ofinhibiting at least 10% precipitation of transition metal complexeswhich would otherwise be insoluble in an aqueous mixture from solutionsby combining said solutions with a polymer comprising the structure ofFormula 1:

-   -   wherein:        -   ε is the site of attachment to a carbon atom in the polymer            backbone, side group, or side chain;        -   R₁ is selected from the group consisting of —H, metal salt            having Na, K, or L₁ cation, amine cation salt, and a            structure of Formula 2:

-   -   -   -   wherein:            -   θ is the site of attachment to Formula 1,            -   R₄ and R₅ are independently selected from the group                consisting of —H, metal salt having Na, K, or L₁ cation,                and amine cation salt;            -   R₂ is selected from the group consisting of —H, metal                salt having Na, K, or Li cation, amine cation salt, and                a structure of Formula 3:

-   -   -   -   wherein:            -   θ is the site of attachment to Formula 1,            -   R₆, and R₇ are independently selected from the group                consisting of —H, metal salt having Na, K, or L₁ cation,                and amine cation salt, and            -   n is an integer from 1 to 22; and            -   R₃ is selected from the group consisting of —H, metal                salt having Na, K, or Li cation, and amine cation salt.

In one embodiment of the method, the polymer further comprises a repeatunit with a structure of Formula 4:

-   -   wherein:        -   ω is the site of attachment to the phosphono-phosphate group            of Formula 1;        -   ψ are the sites of attachment to other repeat units in the            polymer backbone;        -   R₈ is selected from the group consisting of —H and —CH₃;        -   L₁ is selected from the group consisting of a chemical bond,            arenediyl, and a structure of Formula 4:

-   -   wherein:        -   α is the site of attachment to the polymer backbone;        -   β is the site of attachment to the phosphono-phosphate group            of Formula 1;        -   X is selected from the group consisting of the structures in            Formulas 6-Formula 6

-   -   -   wherein:        -   R₉ is selected from the group consisting of —H,            alkyl_((C1-8)), phosphonoalkyl, and            phosphono(phosphate)alkyl; and

    -   Y is selected from the group consisting of alkanediyl,        alkoxydiyl, alkylaminodiyl and alkenediyl.

In one embodiment of the method, the transition metal complexes whichwould otherwise be insoluble comprises one or more multivalent metalcations selected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn,Zn, Fe, and Al.

In one embodiment of the method, the transition metal complexes whichwould otherwise be insoluble comprises one or more anions selected fromthe group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹).

In one embodiment of the method, the aqueous mixture comprises a metalsalt having a monovalent cation.

In one embodiment of the method, the transition metal complexes whichwould otherwise be insoluble comprises one or more multivalent metalcations selected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn,Zn, Fe, and Al and one or more anions selected from the group consistingof F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄ ⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹,SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇ ⁻³, H₂P₂O₇ ⁻², H₃P₂O₇⁻¹, and (PO₃ ⁻¹).

In one embodiment of the method, the transition metal complexes whichwould otherwise be insoluble comprises one or more multivalent metalcations selected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn,Zn, Fe, and Al and one or more anions selected from the group consistingof F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄ ⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹,SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇ ⁻³, H₂P₂O₇ ², H₃P₂O₇ ⁻¹,and (PO₃ ⁻¹), and the aqueous mixture further comprises a metal salthaving a monovalent cation.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, and R₈ is —H.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, and R₈ is —CH₃.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, and L₁ is a chemical bond.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, R₈ is —H, and L₁ is a chemical bond.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, R₈ is —CH₃, and L₁ is a chemical bond.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, and L₁ has the structure of Formula 5 andX has the structure in Formula 6.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, and L₁ has the structure of Formula 5 andX has the structure in Formula 9.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, and L₁ has the structure of Formula 5 andX has the structure in Formula 11.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, and the transition metal complexes whichwould otherwise be insoluble comprises one or more multivalent metalcations selected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn,Zn, Fe, and Al.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, and the transition metal complexes whichwould otherwise be insoluble comprises one or more anions selected fromthe group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄⁻³, HPO₄ ⁻², H₂PO₄ ⁻, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃ ⁻¹, P₂O₇ ⁻⁴, HP₂O₇⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹ and (PO₃ ⁻¹).

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, and the aqueous mixture comprises a metalsalt having a monovalent cation.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, the transition metal complexes whichwould otherwise be insoluble comprises one or more multivalent metalcations selected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn,Zn, Fe, and Al and one or more anions selected from the group consistingof F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄ ⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹,SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻ P₂O₇ ⁻⁴, HP₂O₇ ⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹,and (PO₃ ⁻¹).

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, the transition metal complexes whichwould otherwise be insoluble comprises one or more multivalent metalcations selected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn,Zn, Fe, and Al and one or more anions selected from the group consistingof F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄ ⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹,SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇ ⁻³, H₂P₂O₇ ⁻², H₃P₂O₇⁻¹, and (PO₃ ⁻¹), and the aqueous mixture additionally comprises a metalsalt having a monovalent cation.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, the transition metal complexes whichwould otherwise be insoluble comprises one or more multivalent metalcations selected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn,Zn, Fe, and Al, and R₈ is —H.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, the transition metal complexes whichwould otherwise be insoluble comprises one or more multivalent metalcations selected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn,Zn, Fe, and Al, and R₈ is —CH₃.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, the transition metal complexes whichwould otherwise be insoluble comprises one or more multivalent metalcations selected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn,Zn, Fe, and Al, and L₁ is a chemical bond.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, the transition metal complexes whichwould otherwise be insoluble comprises one or more multivalent metalcations selected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn,Zn, Fe, and Al, R₈ is —H, and L₁ is a chemical bond.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, the transition metal complexes whichwould otherwise be insoluble comprises one or more multivalent metalcations selected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn,Zn, Fe, and Al, R₈ is —CH₃, and L₁ is a chemical bond.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, the transition metal complexes whichwould otherwise be insoluble comprises one or more multivalent metalcations selected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn,Zn, Fe, and Al, and L₁ has the structure of Formula 5 and X has thestructure in Formula 6.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, the transition metal complexes whichwould otherwise be insoluble comprises one or more multivalent metalcations selected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn,Zn, Fe, and Al, and L₁ has the structure of Formula 5 and X has thestructure in Formula 9.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, the transition metal complexes whichwould otherwise be insoluble comprises one or more multivalent metalcations selected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn,Zn, Fe, and Al, and L₁ has the structure of Formula 5 and X has thestructure in Formula 11.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, the transition metal complexes whichwould otherwise be insoluble comprises one or more anions selected fromthe group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F P₂O₇ ⁻⁴, HP₂O₇ ⁻³,H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹), and R₈ is —H.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, the transition metal complexes whichwould otherwise be insoluble comprises one or more anions selected fromthe group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F P₂O₇ ⁻⁴, HP₂O₇ ⁻³,H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹), and R₈ is —CH₃.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, the transition metal complexes whichwould otherwise be insoluble comprises one or more anions selected fromthe group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹), and U is a chemical bond.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, the transition metal complexes whichwould otherwise be insoluble comprises one or more anions selected fromthe group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ and (PO₃ ⁻¹), R₈ is —H, and L₁ is a chemical bond.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, the transition metal complexes whichwould otherwise be insoluble comprises one or more anions selected fromthe group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹), R₈ is —CH₃, and L₁ is a chemicalbond.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, the transition metal complexes whichwould otherwise be insoluble comprises one or more anions selected fromthe group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ and (PO₃ ⁻¹), L₁ has the structure of Formula 5and X has the structure in Formula 6.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, the transition metal complexes whichwould otherwise be insoluble comprises one or more anions selected fromthe group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹), L₁ has the structure of Formula5 and X has the structure in Formula 9.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, the transition metal complexes whichwould otherwise be insoluble comprises one or more anions selected fromthe group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹), L₁ has the structure of Formula5 and X has the structure in Formula 11.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, the transition metal complexes whichwould otherwise be insoluble comprises one or more multivalent metalcations selected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn,Zn, Fe, and Al, one or more anions selected from the group consisting ofF⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄ ⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇ ⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹,and (PO₃ ⁻¹), and R₈ is —H.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, the transition metal complexes whichwould otherwise be insoluble comprises one or more multivalent metalcations selected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn,Zn, Fe, and Al, one or more anions selected from the group consisting ofF⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄ ⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇ ⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹,and (PO₃ ⁻¹), and R₈ is —CH₃.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, the transition metal complexes whichwould otherwise be insoluble comprises one or more multivalent metalcations selected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn,Zn, Fe, and Al, one or more anions selected from the group consisting ofF⁻, Cl⁻, Br⁻, I⁻, OH⁻, S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄ ⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹,SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇ ⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹and (PO₃ ⁻¹), and L₁ is a chemical bond.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, the transition metal complexes whichwould otherwise be insoluble comprises one or more multivalent metalcations selected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn,Zn, Fe, and Al, one or more anions selected from the group consisting ofF⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄ ⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇ ⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹,and (PO₃ ⁻¹), R₈ is —H, and L₁ is a chemical bond.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, the transition metal complexes whichwould otherwise be insoluble comprises one or more multivalent metalcations selected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn,Zn, Fe, and Al, one or more anions selected from the group consisting ofF⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄ ⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇ ⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹,and (PO₃ ⁻¹), R₈ is —CH₃, and L₁ is a chemical bond.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, the transition metal complexes whichwould otherwise be insoluble comprises one or more multivalent metalcations selected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn,Zn, Fe, and Al, one or more anions selected from the group consisting ofF⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄ ⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇ ⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹,and (PO₃ ⁻¹), L₁ has the structure of Formula 5 and X has the structurein Formula 6.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, the transition metal complexes whichwould otherwise be insoluble comprises one or more multivalent metalcations selected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn,Zn, Fe, and Al, one or more anions selected from the group consisting ofF⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄ ⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇ ⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹,and (PO₃ ⁻¹), L₁ has the structure of Formula 5 and X has the structurein Formula 9.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, the transition metal complexes whichwould otherwise be insoluble comprises one or more multivalent metalcations selected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn,Zn, Fe, and Al, one or more anions selected from the group consisting ofF⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄ ⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇ ⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹,and (PO₃ ⁻¹), L₁ has the structure of Formula 5 and X has the structurein Formula 11.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, the transition metal complexes whichwould otherwise be insoluble comprises one or more multivalent metalcations selected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn,Zn, Fe, and Al, one or more anions selected from the group consisting ofF⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄ ⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻ P₂O₇ ⁻⁴, HP₂O₇ ⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and(PO₃ ⁻¹), the aqueous mixture additionally comprises a metal salt havinga monovalent cation, and R₈ is —H.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, the transition metal complexes whichwould otherwise be insoluble comprises one or more multivalent metalcations selected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn,Zn, Fe, and Al, one or more anions selected from the group consisting ofF⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄ ⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇ ⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹,and (PO₃ ⁻¹), the aqueous mixture additionally comprises a metal salthaving a monovalent cation, and R₈ is —CH₃.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, the transition metal complexes whichwould otherwise be insoluble comprises one or more multivalent metalcations selected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn,Zn, Fe, and Al, one or more anions selected from the group consisting ofF⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄ ⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇ ⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹,and (PO₃ ⁻¹), the aqueous mixture additionally comprises a metal salthaving a monovalent cation, and L₁ is a chemical bond.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, the transition metal complexes whichwould otherwise be insoluble comprises one or more multivalent metalcations selected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn,Zn, Fe, and Al, one or more anions selected from the group consisting ofF⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄ ⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇ ⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹,and (PO₃ ⁻¹), the aqueous mixture additionally comprises a metal salthaving a monovalent cation, R₈ is —H, and L₁ is a chemical bond.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, the transition metal complexes whichwould otherwise be insoluble comprises one or more multivalent metalcations selected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn,Zn, Fe, and Al, one or more anions selected from the group consisting ofF⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄ ⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F P₂O₇ ⁻⁴, HP₂O₇ ⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and(PO₃ ⁻¹), the aqueous mixture additionally comprises a metal salt havinga monovalent cation, R₈ is —CH₃, and L₁ is a chemical bond.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, the transition metal complexes whichwould otherwise be insoluble comprises one or more multivalent metalcations selected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn,Zn, Fe, and Al, one or more anions selected from the group consisting ofF⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄ ⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F P₂O₇ ⁻⁴, HP₂O₇ ⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and(PO₃ ⁻¹), the aqueous mixture additionally comprises a metal salt havinga monovalent cation, L₁ has the structure of Formula 5 and X has thestructure in Formula 6.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, the transition metal complexes whichwould otherwise be insoluble comprises one or more multivalent metalcations selected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn,Zn, Fe, and Al, one or more anions selected from the group consisting ofF⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄ ⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇ ⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹,and (PO₃ ⁻¹), the aqueous mixture additionally comprises a metal salthaving a monovalent cation, L₁ has the structure of Formula 5 and X hasthe structure in Formula 9.

In one embodiment of the method, said polymer comprises a repeat unitwith a structure of Formula 4, the transition metal complexes whichwould otherwise be insoluble comprises one or more multivalent metalcations selected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn,Zn, Fe, and Al, one or more anions selected from the group consisting ofF⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄ ⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇ ⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹,and (PO₃ ⁻¹), the aqueous mixture additionally comprises a metal salthaving a monovalent cation, L₁ has the structure of Formula 5 and X hasthe structure in Formula 11.

The present invention further encompasses a method of making a stableaqueous metal salt composition, wherein the method comprises the stepsof dissolving a metal salt comprising one or more multivalent cations inan aqueous solution comprising water to form an aqueous metal saltcomposition, and adding to said aqueous metal salt composition a polymerof the present invention as described in detail herein. The one or moremultivalent metal cations can be selected from the group consisting ofCa, Cu, Ni, Mg, Mn, Sn, Zn, Fe, and Al. The aqueous metal saltcomposition can further comprise one or more anions selected from thegroup consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄ ⁻³,HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F P₂O₇ ⁻⁴, HP₂O₇ ⁻³,H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹). The aqueous metal salt compositioncan further comprise an additional metal salt comprising a monovalentcation. Adding the polymer of the present invention to an aqueous metalsalt composition containing dissolved metal salt comprising multivalentcations can help stabilize the composition by helping to prevent themetal salt comprising multivalent cations from precipitating out ofsolution over time.

Another embodiment of the present invention is an aqueous compositioncomprising a metal salt comprising one or more multivalent cations and apolymer having the structure of Formula 13, where polymer in thiscontext is meant to include oligomers such as dimers, trimers andtetramers:

-   -   wherein:        -   R₁ is selected from the group consisting of —H, metal salt            having Na, K, or L₁ cation, amine cation salt, and a            structure of Formula 2:

-   -   -   -   wherein:            -   θ is the site of attachment to Formula 13,            -   R₄ and R₅ are independently selected from the group                consisting of —H, metal salt having Na, K, or L₁ cation,                and amine cation salt;

        -   R₂ is selected from the group consisting of —H, metal salt            having Na, K, or L₁ cation, amine cation salt, and a            structure of Formula 3:

-   -   -   -   wherein:            -   θ is the site of attachment to Formula 13,            -   R₆, and R₇ are independently selected from the group                consisting of —H, metal salt having Na, K, or L₁ cation,                and amine cation salt, and            -   n is an integer from 1 to 22; and

        -   R₃ is selected from the group consisting of —H, metal salt            having Na, K, or L₁ cation, and amine cation salt;

        -   R₈ is selected from the group consisting of —H and —CH₃;

        -   L₁ is selected from the group consisting of a chemical bond,            arenediyl, and a structure of Formula 5:

-   -   -   -   wherein:                -   α is the site of attachment to the polymer backbone;                -   β is the site of attachment to the                    phosphono-phosphate;                -   X is selected from the group consisting of the                    structures in Formulas 6-12;

-   -   -   -   wherein:                -   R₉ is selected from the group consisting of —H,                    alkyl_((C1-8)), phosphonoalkyl, and                    phosphono(phosphate)alkyl; and                -   Y is selected from the group consisting of                    alkanediyl, alkoxydiyl, alkylaminodiyl and                    alkenediyl, R₁₀ is a chemical group resulting from                    polymer initiation;

        -   R₁₁ is a chemical group resulting chain termination;

        -   M₂ is selected from the group consisting of a chemical bond            and the post polymerization residue of one or more            co-monomers; and

        -   m is an integer from 2 to 450.

In one embodiment of the polymer, R₁₀, the chemical group resulting frompolymer initiation, is selected from the structures of Formula 14-18:

-   -   wherein:        -   R₁₂ is selected from the group consisting of —H, Na, K and            amine cation salt;        -   τ is the site of attachment to polymer backbone and;        -   Q is the non-olefin residue of a monomer used in            polymerization.

In one embodiment of the polymer, M₂ is the polymerization residue ofone or more co-monomers with the structure of Formula 19:

-   -   wherein:        -   R₁₃ is selected from the group consisting of —H or —CH₃;        -   Q₁ is the non-olefin residue of a co-monomer used in            polymerization; and        -   p is an integer from 1 to 450.

In a further embodiment, Q has the structure of Formula 20:

-   -   wherein: L₁, R₁, R₂ and R₃ are as previously noted and K denotes        the site of attachment to Formula 18.

In a further embodiment Q is sulfonate. In a further embodiment Q isphosphonate. In a further embodiment Q is a carboxylate.

In a further embodiment Q₁ is sulfonate. In a further embodiment Q₁ isphosphonate. In a further embodiment Q₁ is a carboxylate.

In one embodiment of the compound, R₁₁, the chemical group resultingfrom polymer termination, is selected from the group consisting of —H.In one embodiment of the compound, R₁₁, the chemical group resultingfrom polymer termination, is another polymer chain with a head to headattachment.

In one preferred embodiment of the compound, R₁, R₂, and R₃ areindependently selected from the group consisting of H, Na salt, K saltand amine cation salt, R₈ is H, L₁ is a covalent bond, R₁₀ is thestructure of Formulas 14-18, and R₁₁ is H.

Methods of Making the Polymers

Embodiments of the present invention can be made using these followinggeneral methods.

The polymers of the present invention can be made by a wide variety oftechniques, including bulk, solution, emulsion, or suspensionpolymerization. Polymerization methods and techniques for polymerizationare described generally in Encyclopedia of Polymer Science andTechnology, Interscience Publishers (New York), Vol. 7, pp. 361-431(1967), and Kirk-Othmer Encyclopedia of Chemical Technology, 3rdedition, 18, pp. 740-744, John Wiley & Sons (New York), 1982, bothincorporated by reference herein. See also Sorenson, W. P. and Campbell,T. W., Preparative Methods of Polymer Chemistry. 2nd edition,Interscience Publishers (New York), 1968, pp. 248-251, incorporated byreference herein, for general reaction techniques suitable for thepresent invention. In one example, the polymers are made by free radicalcopolymerization, using water soluble initiators. Suitable free radicalinitiators include, but are not limited to, thermal initiators, redoxcouples, and photochemical initiators. Redox and photochemicalinitiators may be used for polymerization processes initiated attemperatures below about 30° C. Such initiators are described generallyin Kirk-Othmer Encyclopedia of Chemical Technology, 3rd edition, JohnWiley & Sons (New York), Vol. 13, pp. 355-373 (1981), incorporated byreference herein. Typical water-soluble initiators that can provideradicals at 30° C. or below include redox couples, such as potassiumpersulfate/silver nitrate, and ascorbic acid/hydrogen peroxide. In oneexample, the method utilizes thermal initiators in polymerizationprocesses conducted above 40° C. Water soluble initiators that canprovide radicals at 40° C. or higher can be used. These include, but arenot limited to, hydrogen peroxide, ammonium persulfate, and2,2′-azobis(2-amidinopropane)dihydrochloride. In one example, watersoluble starting monomers are polymerized in a water at 60° C. usingammonium persulfate as the initiator.

The identity of chemical functional groups at the terminal ends of alinear polymer depend upon how the polymerization of that polymer chainwas initiated and terminated. For free radical polymerization, any freeradical in the system can begin a new chain. This free radical can be adirect derivative of the initiator such as a sulfate radical frompersulfate, or alkyl radical from the azo type initiators (such as butnot limited to 2,2′azobis(2-amidinopropane)dihydrochloride). The freeradical can also be the result of a transfer reaction, for instancebetween a water and another radical to produce a hydroxyl radical orbetween a phosphate and another radical to produce a phosphate radical.Non-limiting examples of these resulting structures are given below,where R represents an H or appropriate counter ion such as Na, K or anamine and T represents the site of attachment to the polymer.

The free radical can also be the result of a chain transfer reaction,where the radical is transferred from a growing polymer chain to start anew chain. Chain transfer has been explicitly noted in polymerization ofvinyl phosphonate monomers. Bingöl et al. Macromolecules 2008, 41,1634-1639), incorporated by reference herein, describe howpolymerization of alkyl esters of vinyl phosphonate result in chaintransfer on the alkyl group. This transfer ultimately begins a newpolymer chain with an olefin containing chemical group on the initiatingend. A chain transfer stops growth of one chain and begins a new chain.

In the phosphono-phosphate containing polymers, vinyl CH₂ groups wereobserved in the final polymers compositions. These vinyl groups arehypothesized to form from one of two mechanisms. The first mechanism isa similar phenomenon to that observed by Bingöl, unlike Bingöl, however,the olefin is not from the alkyl ester of phosphonate, but potentiallyfrom the vinyl monomer on the newly initiated chain. Not wanting to bebound by theory, the below scheme is given as a possible route by whichchain transfer could result in an olefin at the site of initiation for ageneric free radical polymerizable monomer where the non-olefin portionof the monomer is simply depicted as Q for clarity. Q can represent anynumber of chemical functional groups and is not limited to a singlechemical entity. Olefin terminated groups based on vinyl phosphonate,and vinyl phosphono-phosphate, have been observed.

The second mechanism to introduce vinyl groups involves a backbitingreaction and beta scission. This mechanism has been extensively notedfor acrylate polymers in the literature. A vinyl group and primaryradical result after beta scission.

Using the previously used nomenclature of using T to represent the siteof attachment to the polymer, the initial functional group can bewritten as follows. It should be noted that both the chain transfer andbackbiting followed by beta scission mechanisms will produce a vinylgroup with two protons on the same carbon atom.

The chemical group on the terminating end of the polymer chain dependsupon how the chain is terminated. The most common terminations are thepreviously mentioned chain transfer, and backbiting reactions as well ascombination and disproportionation. In chain transfer and backbiting,the terminating group is typically a hydrogen. In combination, thepropagating radicals on two chains react to form a new chain. Thisreaction causes a “head to head” configuration at the point ofattachment.

In disproportionation, a hydrogen is exchanged from one radical chain toanother radical chain. The result is one chain is unsaturated while theother is saturated. Of note, the resulting unsaturated group is not avinyl group. Each carbon in the unsaturation has only one hydrogen.

A polymer comprising a phosphono-phosphate group can have thephosphono-phosphate group attached directly off the polymer backbone, ona side group, or on a side chain. This phosphono-phosphate group can beincorporated into the polymer by either polymerization of monomershaving the phosphono-phosphate group, or by polymerization of monomerswithout a phosphono-phosphate group and subsequent post-polymerizationmodification of the resulting polymer to add the phosphono-phosphategroup. While the examples in the subsequent paragraphs will depicthomopolymers for simplicity, it is understood that polymers withadditional monomers besides phosphonate or phosphono-phosphatecontaining monomers could be made by including these other monomers inthe polymerization process.

As examples of polymers comprising a phosphono-phosphate group attachedto a polymer backbone, consider the polymers made from the monomersvinyl phosphonate or methyl-vinyl phosphonate. Vinyl phosphonate ormethyl-vinyl phosphonate can be chemically reacted to formphosphono-phosphate monomers as shown in reaction 1 in Scheme 1. Thesephosphono-phosphate containing monomers can then be polymerized as shownin reaction 2 of the same scheme to yield a phosphono-phosphatecontaining polymer with the phosphono-phosphate group attached directlyto the polymer backbone. Alternatively, vinyl phosphonate ormethyl-vinyl phosphonate can be first polymerized as shown in reaction 3to yield a polymer. After polymerization, the phosphono-phosphate groupcan be created by post-polymerization modification by reacting theattached phosphonate moiety as shown in reaction 4 thus creating aphosphono-phosphate group attached directly to the polymer backbone.

A second manner of creating a phosphono-phosphate group attacheddirectly to the backbone by a post polymerization modification can beexemplified by starting with polyethylene. For an example of the firstreaction in such a modification, see M. Anbar, G. A. St. John and A. CScott, J Dent Res Vol 53, No 4, pp 867-878, 1974. As shown in Scheme 2,polyethylene is first phosphorylated oxidatively with oxygen and PCl₃ toform a randomly phosphonated polymer. This phosphonated polymer can thenbe modified to produce a randomly substituted phosphono-phosphatepolymer. The reaction products shown are meant to show the random natureof the points of attachment of the phosphono-phosphate groups of theresulting polymer.

As an example of the production of polymers having a phosphono-phosphategroup attached to a side group, consider the vinyl benzyl chemistrydepicted in Scheme 3. As with the previous example, this scheme willdepict homopolymers for simplicity. However, heteropolymers havingadditional monomeric constituents could be made by including additionalmonomers in the polymerization process. 4-Vinylbenzyl chloride can bereacted with diethyl phosphite to form vinyl benzyl phosphonate depictedin reaction 1 of Scheme 3. For an example of this reaction, see Frantz,Richard; Durand, Jean-Olivier; Carre, Francis; Lanneau, Gerard F.; LeBideau, Jean; Alonso, Bruno; Massiot, Dominique, Chemistry—A EuropeanJournal, Volume 9, Issue 3, pp. 770-775, 2003. Vinyl benzyl phosphonatecan be reacted to form vinyl benzyl phosphono-phosphate shown inreaction 2, as described in the example section below. This monomer canthen be polymerized, as described in the example section below, to forma phosphono-phosphate containing polymer depicted by reaction 5, inwhich the phosphono-phosphate group is attached to a side group on thepolymer. Alternatively, the first intermediate, vinyl benzylphosphonate, can be polymerized shown in reaction 4 to make poly vinylbenzyl phosphonate. For an example of this reaction, see M. Anbar, G. A.St. John and A. C Scott, J Dent Res Vol 53, No 4, pp 867-878, 1974. Polyvinyl benzyl phosphonate can then be reacted as shown in reaction 7 toproduce a phosphono-phosphate containing polymer where thephosphono-phosphate group is attached to a side group on the polymer bya post polymerization modification described in the example sectionbelow. A second route involving a post polymerization modification isalso shown in the same scheme. 4-Vinylbenzyl chloride can be polymerizedto provide poly vinyl benzyl chloride shown in reaction 3. This polymercan be phosphonated shown in reaction 6 (for example, see Sang Hun Kim,Young Chul Park, Gui Hyun Jung, and Chang Gi Cho, MacromolecularResearch Vol 15 No 6 pp 587-597, 2007), and then the resulting polyvinyl benzyl phosphonate reacted to produce the phosphono-phosphatecontaining polymer shown in reaction 7.

As a first example of polymers comprising a phosphono-phosphate groupattached to a side chain, consider the poly ethylene glycol (PEG) sidechains depicted in Scheme 4. A phosphonate containing PEG chain can bereacted with acryl chloride to produce an acrylic ester with an PEGterminated phosphonate. After reaction to produce a phosphono-phosphate,the phosphono-phosphate monomer can be polymerized to produce aphosphono-phosphate containing polymer where the phosphono-phosphate isattached to a side chain of the polymer.

As a second example of polymers comprising a phosphono-phosphate groupattached to a side chain, consider the poly vinyl alcohol depicted inScheme 5. The hydroxyl groups can be reacted with ethylene oxide toproduce a polymer with PEG side chains. The terminating hydroxy on theside chains can be reacted with vinyl phosphonate, and then reacted toform a phosphono-phosphate. This example thus depicts aphosphono-phosphate containing polymer where the phosphono-phosphate isattached to a side chain of the polymer and is added via a postpolymerization modification.

The schemes depicted are not meant to be exhaustive in nature, but aremeant to convey the various manners in which phosphono-phosphatecontaining polymers may be produced. The examples provide both technicaldetails for synthesis and numerous variations of polymers containingphosphono-phosphate groups, both polymers with phosphono-phosphategroups attached directly to the polymer backbone and polymers withphosphono-phosphate groups attached to side groups. For further examplesof phosphonate containing monomers and polymers that can be transformedinto phosphono-phosphonate containing monomers and polymers, see SophieMonge, Benjamin Canniccioni, Ghislain David and Jean-Jacques Robin, RSCPolymer Chemistry Series No. 11, Phosphorus-Based Polymers: FromSynthesis to Applications, edited by Sophie Monge and Ghislain David,The Royal Society of Chemistry 2014, Published by the Royal Society ofChemistry, www.rsc.org.

Uses of the Phosphono-Phosphate Containing Polymers

The phosphono-phosphate containing polymers with multi-valent cationsaccording to the present invention can be incorporated into a variety ofcompositions. These compositions include both aqueous and non-aqueouscompositions. The compositions are useful for treating teeth, hair,body, fabric, paper, non-wovens and hard surfaces. The compositions findutility in water treatments, boiler treatments, treating ship hulls, oilwells, batteries, baking, leavening, ceramics, plastics stabilizers,glass manufacture, cheese production, buffers in food, abrasives indentifrice, binders in meat, coffee creamers, antifreeze, dispersingagents in paints liquid soaps, metal cleaners synthetic rubber, textilesand flame retardants. The compositions are also useful for treatingmaterials containing multivalent metal cations including but not limitedto calcium, tin, magnesium and iron. Examples of such materials includehydroxyapatite, calcium carbonate (amorphous, calcite, aragonite),calcium phosphate, calcium hydroxide, magnesium carbonate, magnesiumphosphate, soap scum (mixture of calcium, magnesium, and iron salts ofstearic acid and carbonate), and hard water stains. In one embodiment,the composition comprising phospho no-phosphate containing polymers isnon-aqueous. In another embodiment, the composition is aqueous.

The phosphono-phosphate containing compounds and polymers can be appliedto a variety of substrates. Embodiments of substrates include biologicalmaterial, fabric, non-woven materials, paper products, and hard surfacematerials. In one embodiment, the biological material comprises teeth.In another embodiment, the biological material comprises keratin, suchas hair or skin.

EXAMPLES

The following examples further describe and demonstrate the preferredembodiments within the scope of the present invention. The examples aregiven solely for the purpose of illustration and are not to be construedas limitations of the present invention since many variations thereofare possible without departing from the spirit and scope of theinvention. Ingredients are identified by chemical name, or otherwisedefined below.

Example 1—Synthesis of Vinyl Phosphono-monoPhosphate (VPP) or[Vinylphosphonic Phosphoric Anhydride]

A magnetically stirred dry 500 ml 1 neck round bottom flask was chargedwith vinyl phosphonic acid (VPA, 25.0 g, 231.5 mmole) and 300 ml DMFunder nitrogen. The resulting mixture was stirred for 10 minutes at roomtemperature yielding a homogenous solution. The tributylamine (64.3 g,82.7 ml, 1.5 equivalents) was added and stirred 30 min at roomtemperature yielding a turbid solution that separated into a small upperlayer and bulk lower layer on standing.

A second magnetically stirred dry 1000 ml 1 neck round bottom flaskfitted with an addition funnel and under nitrogen was charged1,1′-Carbonyldiimidazole (CDI), (45.1 g, 1.2 equivalents) followed by300 ml DMF. The resulting mixture was stirred 10 min at room temperatureyielding a homogenous solution. Next, the tributylamine/vinyl phosphonicacid solution was added to the CDI solution via the addition funnel overapproximately two hours and the resultant mixture was stirred at roomtemperature overnight yielding a light yellow homogenous solution.

A third magnetically stirred 2000 mL 3 neck round bottom flask fittedwith an addition funnel was charged with H₃PO₄ (56.7 g, 2.5 equivalents)followed by 400 ml DMF under nitrogen. Resulting mixture was stirred for15 min at room temperature yielding a homogenous solution. To thismixture was added tributylamine (128.7 g, 165.4 ml, 3.0 equivalents) andthe resultant was stirred 30 min yielding a turbid solution. To thisturbid solution was added the solution from the second flask overapproximately 2 hours via the addition funnel. The resultant was stirredovernight at room temperature to yield a light yellow turbid solution.This solution was stripped of solvent under vacuum (13 Torr) to a finaltemperature of approximately 70° C. to yield 226 g light yellow syrup.

The resultant was dissolved in 450 ml of water and the pH was adjustedto 10.5 with 50% NaOH (˜110 g) yielding 2 phase system. The loweraqueous phase was separated from the upper organic phase. The aqueousphase was stripped of water to a final temperature of approximately 70°C. and vacuum of 13 Torr to yield 212 g of a yellow oil. This oil washeated to approximately 60° C. and 300 ml MeOH was added over 5 min toyield a white precipitate. The MeOH was decanted from the precipitatewhich was dried to 150.6 g in an oven. P-NMR on the precipitate showedthe anticipated phosphono-monophosphate product with 1.22 molarequivalents of orthophosphate, 0.29 equivalents of pyro-phosphate and0.05 molar equivalents of starting vinyl phosphonic acid. H-NMR alsoshowed product, starting material, residual solvents and approximately0.4 molar equivalents imidazole. For further purification, theprecipitant was dissolved in 300 ml water. Under rapid stirring, 400 mlof MeOH was added over 30 minutes. The resulting white precipitant wascollected by filtration, rinsed with 100 ml MeOH and dried overnight toyield 102.4 g. P-NMR's on this precipitant showed it to be primarilyorthophosphate with 0.06 mole equivalents of phosphono-monophosphateproduct and 0.29 mole equivalents of pyrophosphate.

The water MeOH filtrate was stripped of solvent to a final temperatureof approximately 70° C. and pressure of 13 Torr to yield 81.94 g whitesolid. This solid was shown to be primarily vinylphosphono-monophosphate with 0.077 molar equivalents of vinylphosphonate and 0.091 molar equivalents of orthophosphate. Residualimidazole was extracted from this white solid by rapid stirring thesolid in 300 ml MeOH at 40° C. 1 hr, filtering off the insoluble solidswhile the solution was hot, then rinsing the resulting solids twice with50 ml of room temperature MeOH and drying the resultant solid under highvacuum overnight at room temperature to yield 54.8 g of white powder.P-NMR on this final sample showed vinyl phosphono-monophosphate with0.05 molar equivalents of orthophosphate, 0.04 equivalents ofpyrophosphate and 0.02 equivalents of vinyl phosphonate. The H-NMR wasconsistent with vinyl phosphono-monophosphate product with 0.02 molarequivalents of imidazole and 0.09 equivalents of methanol. Using aninternal standard, the total active was calculated to be 80.8%, whichrepresents a yield of 82%.

Example 2—Synthesis of Methyl-Vinyl Phosphono-monoPhosphate (MVPP) or[Methyl Vinyl Phosphonic Phosphoric Anhydride]

The procedure of Example 1 was followed with the substitution ofmethyl-vinyl phosphonic acid for vinyl phosphonic at 1/14 molar scale ofExample 1. Final purity was 71.9% and yield was 31.2%.

Example 3—Synthesis of (Methylenyl Phosphono-MonoPhosphate)-Methacrylate [or ((Methacryloyloxy)Methyl)PhosphonicPhosphoric Anhydride]

A magnetically stirred dry 50 ml 1 neck round bottom flask was chargedwith (Methylenyl Phosphonic Acid)-Methacrylate (0.5 g, 2.77 mmole) and10 ml DMF under nitrogen. The resulting mixture was stirred for 10minutes at room temperature yielding a homogenous solution. Thetributylamine (0.77 g, 1.0 ml, 1.5 equivalents) was added and stirred 30min at room temperature yielding a homogeneous solution.

A second magnetically stirred dry 10 ml 1 neck round bottom flask fittedunder nitrogen was charged 1,1′-Carbonyldiimidazole (CDI), (0.54 g, 1.2equivalents) followed by 10 ml DMF. The resulting mixture was stirred 10min at room temperature yielding a homogeneous solution. Next, thetributylamine/(Methylene Phosphonic Acid)-Methacrylate solution wasadded to the CDI solution over 1 minute and the resultant mixture wasstirred at room temperature 4 hours yielding a light yellow homogeneoussolution.

A third magnetically stirred 50 mL 1 neck round bottom flask was chargedwith H₃PO₄ (0.68 g, 2.5 equivalents) followed by 15 ml DMF undernitrogen. Resulting mixture was stirred for 15 min at room temperatureyielding a homogeneous solution. To this mixture was added tributylamine(1.54 g, 2.0 ml, 3.0 equiv.) and the resultant was stirred 30 minyielding a turbid solution. To this turbid solution was added thesolution from the second flask over 1 minute. The resultant was stirredovernight at room temperature to yield a light yellow turbid solution.This solution was stripped of solvent under vacuum (13 Torr) to a finaltemperature of approximately 65° C. to yield 24.5 g light yellow syrup.

The resultant was dissolved in 100 ml of water and the pH was adjustedto 8 with 1N NaOH (14 g) yielding a milky white system, which wassubsequently concentrated at 65° C. and 13 Torr to 24.5 g of lightyellow syrup. This syrup was added to 50 ml MeOH was added over 5 min toyield a white precipitate. The MeOH was decanted to remove theprecipitate, then the MeOH was stripped under vacuum to yield 7.4 g ofgelatinous solids. P-NMR on the gelatinous solids showed the anticipatedphosphono-monophosphate product with 1 equivalent product, 0.55 molarequivalents of orthophosphate, 0.40 equivalents of the anhydride ofstarting phosphonate.

The bulk of gelatinous solids was stirred in 50 ml EtOH 1 hr at RTyielding an insoluble ppt. The ppt was filtered, rinsed twice with 10 mLof fresh EtOH and hood dried O/N to 238 mg solids. The P-NMR of thesolids showed product peaks doublets (1.1/1.0 ppm & −8.4/−8.5 ppm),phosphate (2.04 ppm), product anhydride (2.9 ppm) in a ratio of100:70:10 as well as other minor unknowns. The H-NMR shows the driedsolids to be consistent with product containing ˜12 mole % imidazole,residual EtOH and other minor unknowns.

Example 4—Synthesis of (Ethyl Phosphono-monoPhosphate) (Butyl)Acrylamide or [(2-(N-Butylacrylamido)Ethyl)Phosphonic PhosphoricAnhydride]

A magnetically stirred dry 25 ml 2 neck round bottom flask was chargedwith n-butylamine (6.3 mL, 63 mmole) and heated under dry nitrogen to78° C. Diethyl vinyl phosphonate (1.0 ml, 6.3 mmole) was added andstirred overnight. Resulting mixture was rotary evaporated at around 45°C. and 20 mbar to recover 1.38 g of material at high purity diethylethyl phosphonate butyl amine by P-NMR (92% recovery).

A magnetically stirred dry 25 ml 2 neck round bottom flask was chargedwith diethyl ethyl phosphonate butyl amine (1.1 g, 4.6 mmole), 2 mL ofdichloromethane and 6 mL of 1N NaOH. Resultant was stirred and cooled inan ice bath. A mixture of 2 mL of dichloromethane and 0.368 g ofacryloyl chloride was added dropwise to this flask over 30 minutes.Resultant was diluted with 10 mL of dichloromethane extracted in aseparatory funnel 2×25 mL 1N HCl, 1×25 mL saturated NaCl with 10 mLrinses with dichloromethane of the aqueous phases. Resulting combinedorganic phases were dried over anhydrous sodium sulfate and filtered.Solvent was removed by rotary evaporation at approximately 35° C. toyield 0.84 g (72%) of product.

The ethyl ester groups on this product were removed by dissolving theentire lot in 4 mL of dichloromethane in a magnetically stirred 100 mL 2neck flask under dry nitrogen in an iced bath then adding a mixture of 1mL dichloromethane and 2 mL of trimethyl bromo silane over 20 minutes.An additional 1 mL of dichloromethane and then a mixture of 1 mL ofdichloromethane and 1 mL of trimethyl bromo silane were then added.After 2 hours, 30 mL of MeOH was added and allowed to stir for 10minutes followed by 0.21 mg of butylated hydroxy toluene in 1 mLdichloromethane. Volatiles were removed by rotary evaporate at around40° C. Resultant was purified by dissolving in 50 mL of dichloromethaneand extracting with a mixture of 25 mL of 0.1 N NaOH and 25 mL of 1 NNaOH. Aqueous phase was extracted a second time with 25 mL ofdichloromethane than acidified with to pH 1 with 1N HCl then rotaryevaporated to near dryness. Resulting residue was diluted with 50 mL ofEtOH and rotary evaporated to near dryness 3 times to remove the water.Resultant residue was then diluted with 10 mL of pentane and evaporatedto near dryness 2 times to remove residual EtOH. Final recovery nearquantitative.

Addition of the phosphono-phosphate group was performed as in Example 3.The purification step was slightly modified. A diethyl ether (1 volumeequivalent) extraction was performed on the crude reaction mixture thenthe solution was vacuum stripped at 30-35° C. Residues were dissolved in25 mL of water and the pH adjusted to 7 with 1N NaOH followed by vacuumstripping of water at 40-45° C. to leave a liquid residue. Next, 100 mLof methanol was added to the residue resulting in a precipitant that wascollected and dried under vacuum to yield approximately 9.1 grams at 80%active by P-NMR.

Example 5—Synthesis of (4-VinylBenzyl) Phosphono-monoPhosphate or[(4-Vinylbenzyl)Phosphonic Phosphoric Anhydride]

A magnetically stirred dry 50 ml 1 neck round bottom flask was chargedwith (4-VinylBenzyl) Phosphonic Acid (4.0 g, 20.2 mmole) and 20 ml DMFunder nitrogen. The resulting mixture was stirred for 10 minutes at roomtemperature yielding a homogenous solution. The tributylamine (5.6 g,7.2 ml, 1.5 equivalents) was added and stirred 30 min at roomtemperature yielding a homogenous solution.

A second magnetically stirred dry 10 ml 1 neck round bottom flask fittedunder nitrogen was charged 1,1′-Carbonyldiimidazole (CDI), (4.9 g, 1.2equivalents) followed by 25 ml DMF. The resulting mixture was stirred 10min at room temperature yielding a homogeneous solution. Next, thetributylamine/(4-VinylBenzyl) Phosphonic Acid solution was added to theCDI solution over 1 minute and the resultant mixture was stirred at roomtemperature 4 hours yielding a light yellow homogeneous solution.

A third magnetically stirred 100 mL 1 neck round bottom flask wascharged with H₃PO₄ (5.94 g, 3.0 equivalents) followed by 25 ml DMF undernitrogen. Resulting mixture was stirred for 15 min at room temperatureyielding a homogeneous solution. To this mixture was added tributylamine(13.1 g, 16.8 ml, 3.5 equivalents) and the resultant was stirred 30 minyielding a turbid solution. To this turbid solution was added thesolution from the second flask over 1 minute. The resultant was stirredovernight at room temperature to yield a light-yellow solution. Thissolution was stripped of solvent under vacuum (13 Torr) to a finaltemperature of approximately 65° C. to yield 49.8 g light yellow syrup.

The resultant was added to 30 ml of water and the pH was adjusted to 8.5with 1N NaOH (˜127 g) yielding a milky white system, which wassubsequently concentrated at 65° C. and 13 Torr to 58.2 g of lightyellow syrup. This syrup was added to 40 ml MeOH was added over 20 minto yield a white precipitate. P-NMR on the paste showed it to beapproximately 95% phosphate. The MeOH was decanted to remove theprecipitate, then the MeOH was stripped to yield 7.23 g of white paste.The P NMR on the white paste showed the anticipatedphosphono-monophosphate product with 1 equivalent product, 0.16 molarequivalents of orthophosphate, 0.05 equivalents of pyrophosphate, 0.25equivalents of the anhydride of starting phosphonate and 0.065equivalents of starting phosphonate.

The bulk of the white paste was stirred in 75 ml MeOH 1 hr at roomtemperature. A portion of the paste dissolved, however a portionremained insoluble. The insoluble portion was filtered and rinsed twicewith 10 mL of fresh MeOH. The resulting solid was dried under highvacuum O/N to yield 1.97 g solids. The P-NMR of the solids showedproduct peaks doublets (1.1/1.0 ppm & −8.4/−8.5 ppm), phosphate (2.04ppm), product anhydride (2.9 ppm) in a ratio of 100:70:10 as well asother minor unknowns. The H-NMR shows the dried solids to be consistentwith product containing ˜12 mole % imidazole, residual EtOH and otherminor unknowns. The yield of the final solids was 23.7% of theoretical.

Example 6—Synthesis of (Bis(Methylene PhosphonateAnhydride)Aminopropyl)-Methacrylate Polymer or[4-(3-(Methacryloyloxy)Propyl)-1,4,2,6-Oxazadiphosphinane-2,6-Bis(Olate)2,6-Dioxide Polymer]

A magnetically stirred dry 250 ml 3 neck round bottom flask was chargedwith (Bis(Methylene Phosphonic Acid)aminopropyl)-Methacrylate (3.0 g,9.06 mmole) and 100 ml DMF under nitrogen. The resulting mixture wasstirred for 10 minutes at room temperature yielding a homogenoussolution. The tributylamine (5.03 g, 6.5 ml, 3.0 equivalents) was addedand stirred 30 min at room temperature yielding a homogeneous solution.

A second magnetically stirred dry 100 ml 1 neck round bottom flaskfitted with an addition funnel and under nitrogen was charged1,1′-Carbonyldiimidazole (CDI), (2.2 g, 1.5 equivalents) followed by 40mL DMF. The resulting mixture was stirred 10 min at room temperatureyielding a homogenous solution. The CDI solution was added via additionfunnel over approximately one hour to the first flask and the resultantmixture was stirred at room temperature overnight followed by standingfor 1 week to yield a white precipitate. The precipitant was collectedby filtration, slurried in 100 mL water and the pH adjusted to ≈9 with1N NaOH yielding a turbid solution. This solution was evaporatedovernight under flowing air to 2.4 g. The H & P-NMR's showed theprecipitant to be polymer with some monomer. The P-NMR showed polymerictarget anhydride (at 12-13 ppm) and starting di-acid (at 6-7 ppm) aswell as monomer peaks (at 11.8-12 ppm) in a ratio of 36:53:11. The bulkof the precipitant was sonicated in 100 mL water 1 hr yielding a turbidsolution which was filtered using a 250 mL Stericup Durapore with 0.22μm PVDF filter disk yielding a clear solution. This was brought up to250 ml and purified by dialysis in a Thermo Scientific Slide-A-Lyzerdialysis flask (2K MWCO, 250 ml) against 5 gallons RO water (pH adjustedto 8.5 w 1N NaOH) for 7 days yielding 1.29 g white solid (17-DF-5835-5)after freeze drying. The P-NMR showed a broad anhydride peak at 12-13ppm & a di-acid peak at 6.4-7.4 ppm in a 39.2:60.8 molar ratio. Activitywas calculated to be 87.8% polymer & 12.2% water/inactives

Example 7—Synthesis of (Ethyl Phosphono-Monophosphate)-Methacrylate or[(2-(Methacryloyloxy)Ethyl)Phosphonic Phosphoric Anhydride]

A magnetically stirred dry 100 ml 1 neck round bottom flask was chargedwith (Ethyl Phosphonic Acid)-Methacrylate (3 g, 15.5 mmole) and 30 mlDMF under nitrogen. The resulting mixture was stirred for 10 minutes atroom temperature yielding a homogeneous solution. The tributylamine (4.3g, 5.5 ml, 1.5 equivalents) was added and stirred 30 min at roomtemperature yielding a homogeneous solution.

A second magnetically stirred dry 25 ml 1 neck round bottom flask fittedunder nitrogen was charged 1,1′-Carbonyldiimidazole (CDI), (3.76 g, 1.5equivalents) followed by 20 ml DMF. The resulting mixture was stirred 10min at room temperature yielding a homogeneous solution. Next, thetributylamine/(Ethyl Phosphonic Acid)-Methacrylate solution was added tothe CDI solution and the resultant mixture was stirred at roomtemperature 4 hours yielding a light yellow homogeneous solution.

A third magnetically stirred 500 mL 1 neck round bottom flask wascharged with H₃PO₄ (4.55 g, 3.0 equivalents) followed by 25 ml DMF undernitrogen. Resulting mixture was stirred for 15 min at room temperatureyielding a homogeneous solution. To this mixture was added tributylamine(12 g, 15.4 ml, 4.2 equiv.) and the resultant was stirred 30 minyielding a turbid solution. To this turbid solution was added thesolution from the second flask over 1 minute. At about 1 hour ofstirring, a white precipitant began to form. The resultant was stirredovernight at room temperature with additional precipitant forming. TheP-NMR showed product peaks doublets (7.2/7.3 ppm & −8.75/−8.84 ppm),phosphate (2.14 ppm), product anhydride (8.9 ppm) & pyrophosphate (−9.26ppm) in a ratio of 100:427:12:15.

To the crude Rx solution (≈90.7 g) was added with stirring 200 mL ethylether over 30 min yielding a white ppt which was collected byfiltration, rinsed with additional ether and dried overnight undervacuum (<1 Torr) at room temperature to yield 7.85 g white precipitant.To the resultant filtrate was added an additional 200 mL ethyl etherwith stirring over 30 min yielding a two-layer system with a freeflowing top layer and lower viscous oil layer. The top layer wasdecanted, and the lower oil layer dried overnight under vacuum (<1 Torr)at room temperature to 2.33 g waxy solid. To the decanted layer wasadded an additional 400 ml ether over 30 min with stirring yielding aturbid solution. The turbid solution was placed in a freezer (−15° C.)overnight yielding a clear free flowing top layer and a viscous oillower layer. The top layer was decanted, and the lower oil layer driedovernight under vacuum (<1 Torr) at room temperature to 1 hr to 1.19 gwaxy solid.

The white precipitant was shown by H-NMR to be a mixture ofproduct:imidazole:tributyl amine in a molar ratio of 100:1150:220, whilethe P-NMR showed a mixture of product:phosphate:pyro in a molar ratio of100:625:35.

The first waxy solid was shown by H-NMR to be a mixture ofproduct:imidazole:tributyl amine in a molar ratio of 100:230:170. TheP-NMR showed a mixture of product:phosphate in a molar ratio of 100:89.

The second waxy solid was shown by H-NMR to be a mixture ofproduct:imidazole:tributyl amine in a molar ratio of 100:100:150. TheP-NMR showed a mixture of product:phosphate in a molar ratio of 100:79.

Waxy solids were combined and dissolved in 50 mL deionized water. The pHof the resultant solution was adjusted from 2.9 to 8.6 with 19.3 g 1NNaOH yielding a turbid solution. This solution was extracted IX with 50mL ethyl ether. The resultant aqueous layer had a pH=7.5 was trimmed to8.0 with additional 1N NaOH. Residual ether was removed from the aqueouslayer on roto-vap at room and 20 Torr. The water was removed from theaqueous layer via freeze-drying yielding 2.61 g tan solid.

The H & P-NMR's showed a mixture of product:imidazole:NBut3 in a molarratio of 100:160:50. The P-NMR shows a mixture of product:phosphate in amolar ratio of 100:101. Tan solid was stirred in 50 mL MeOH for 30 minyielding an insoluble solid. Solid was collected by filtration, rinsed2×10 ml fresh MeOH and dried overnight at room temperature at <1 Torr toyield 1.79 g cream colored solid. The H-NMR's was consistent withproduct containing ˜1 mole % imidazole. The LCMS demonstrated a massconsistent with the M+H protonated form at 273. The H-NMR of methanolextract showed it to be primarily imidazole containing ˜3 mole %product.

Activity was calculated by combined H-NMR and P-NMR and found to be74.4%.

Example 8—Synthesis of (Propyl Phosphono-Monophosphate)-Methacrylate or[(3-(Methacryloyloxy)Propyl)Phosphonic Phosphoric Anhydride]

The procedure of Example 7 was followed substituting 5.5 g (26.4 mmol)(Propyl Phosphonic Acid)-Methacrylate for (Ethyl PhosphonicAcid)-Methacrylate. All reagents were scaled to keep the molarequivalence the same. After final evaporation, 5.17 g of cream solid wascollected and shown to be 67.8% active.

Example 9—Synthesis of (Ethyl Phosphono-monoPhosphate)-Acrylamide or[(2-Acrylamidoethyl)Phosphonic Phosphoric Anhydride]

The procedure of example 5 was followed using (acrylamido)ethylphosphonic acid (37 mmoles) in place of vinyl benzyl phosphonate forcreation of the crude yellow solution, with increased quantities of allreagents at equivalent molar ratios to example 5.

The purification procedure of the crude solution was modified fromexample 5. DMF was partially removed at room temperature with flowingdry nitrogen to yield 46.8 g of a viscous yellow oil. This oil wasdissolved in 75 mL of water and the pH adjusted to 8 by addition of 1 NNaOH over 20 minutes. A small organic layer 9.4 g of tributyl amineformed and was decanted. The aqueous phase was further dried underflowing dry nitrogen to 147.5 g, then 220 mL of MeOH was added over 30minutes to yield a white precipitate. The precipitate was filtered andthe resulting filtrate dried yield 22.7 g of brown paste, which P NMRshowed to be mostly product. The brown paste was slurried in 100 mL ofEtOH under vigorous stirring for 6 hours at room temperature. A solidformed and was collected by filtration, rinsed with fresh EtOH 2×25 mLand dried at <1 Torr overnight to yield 10.94 g of tan solid. The solidcontained 69% phosphono-monophosphate product by NMR.

Example 10—Synthesis of (Methylene Phosphono-Mono Phosphate)-Acrylate or[((Acryloyloxy(Methyl)Phosphonic Phosphoric Anhydride]

The procedure of Example 3 is followed substituting (MethylenePhosphonic Acid)-Acrylate for (Methylene Phosphonic Acid)-Methacrylate

Example 11—Synthesis of (Ethyl Phosphono-monoPhosphate)-Vinyl Ether or[(2-(Vinyloxy(Ethyl(Phosphonic Phosphoric Anhydride]

A dry, septum sealed, nitrogen flushed, magnetically stirred 250 mLthree neck round bottom flask ‘ ’ was charged with diethyl(2-(vinyloxy)ethyl)phosphonate (3 g, 14.4 mmol) and 30 ml CH₂Cl₂ andchilled to 0-5° C. To this flask was added bromotrimethylsilane (5.7 mL,43.2 mmol, 3.0 equivalents) over 1 minute. After addition the solutionwas stirred for 2 hours at room temperature and the solution stripped ofsolvent at 30° C. and <1 Torr to yield 4.59 g yellow oil. To this wasadded 15 g of triethylamine, 30 g MeOH and 60 mg of phenothiazine(inhibitor) that had been pre-chilled over dry ice and acetone.Resultant was allowed to warm to room temperature under constantstirring, then put under vacuum at room temperature to remove solventand volatiles for 1 hour yielding 3.84 g of viscous turbid yellow oil.P-NMR and H-NMR were consistent with amine mono-triethyl amine salt.

The procedure of Example 7 was followed to create and purify (EthylPhosphono-monoPhosphate)-Vinyl Ether resulting in 4.04 g of tan solidafter methanol extraction. The H-NMR's was consistent with productcontaining ˜5 mole % imidazole. The P-NMR was consistent with a productphosphono-monophosphate to residual phosphate ratio of 100:112. The LCMSdemonstrated a mass consistent with the M+H protonated form at 231.Activity was calculated by combined H-NMR and P-NMR and found to be 52%

Example 12—Synthesis of (Ethyl Phosphono-Monophosphate)-Acrylate or[(2-(Acryloyloxy)Ethyl)Phosphonic Phosphoric Anhydride]

A dry magnetically stirred 1L three neck round bottom flask was chargedwith dimethyl (2-hydroxyethyl)phosphonate (24.7 g, 16 mmol), triethylamine (17.8 g 176 mmol) and 400 ml CH₂Cl₂ and chilled to 0-5° C. To thisflask was added a solution of the acryloyl chloride (14.95 g 16.51mmole) in 100 ml CH₂Cl₂ over 1.5 hours while maintaining reactiontemperature of 0-5° C. After the addition was complete the reaction tempwas maintained at 0-5° C. for an additional 2 hours followed by warmingto RT and stirring overnight.

The resulting light brown turbid solution was extracted 2×200 mldeionized water, and the oil layer dried over anhydrous MgSO₄ and thenfiltered. The filtrate was stripped of solvent yielding 30.5 g brownoil. The H, C & P-NMR's were consistent with the first intermediate,(Ethyl, dimethyl phosphonate)-Acrylate. The yield was 91.4%.

The above brown oil was charged into a dry magnetically stirred 500 mLthree neck round bottom flask with 250 mL of dichloromethane. The flaskand contents were chilled to 10° C. and 67.3 g (3 equivalents) ofbromotrimethylsilane was added over 30 minutes. The flask was allowed towarm to room temperature and stirred overnight. Resultant solution wasstripped of solvent at 30° C. followed by stirring under high vacuum (<1Torr) overnight to yield 37 g of light oil. To the oil, 200 mL ofmethanol was added over 10 minutes at room temperature followed bystirring at room temperature for 3 hours. Resultant solution wasstripped of solvent at 30° C. followed by stirring under high vacuum (<1Torr) overnight to yield 26.1 g of a viscous tan oil. H NMR and P NMRwere consistent with product. The yield was 98.9%.

The procedure of example 5 was followed using (acryloyloxyethylphosphonic acid in place of vinyl benzyl phosphonate for creation of thecrude yellow solution. P NMR and H NMR showed 72% yield of desiredproduct.

Example 13—Synthesis of Mixed Vinyl Phosphono-Phosphates

The procedure of Example 1 was followed with the substitution ofpyrophosphoric acid for phosphoric acid at 1/12 molar scale ofExample 1. After removal of the DMF solvent to yield a yellow oil andaddition of 1N NaOH, 24.1 g of white solid was collected after spargingovernight with nitrogen. This sample was shown by PNMR to contain vinylphosphono-pyrophosphate (VPPP), vinyl phosphono-monophosphate, startingmaterial, starting material anhydride, phosphate, pyrophosphate andtriphosphate. The ratio of vinyl phosphono pyrophosphate:vinylphosphono-monophosphate was 1:1.7.

Example 14 Synthesis of Vinyl Sulfonate Methyl Ester (VSME)

A magnetically stirred dry 500 ml 3 neck round bottom flask equippedwith an addition funnel and a thermometer was charged with 250 mL ofmethanol under nitrogen and cooled to 0° C. The 2-chloroethanesulfonylchloride (Aldrich) was added to the flask over 15 minutes with noobserved exotherm. Next 25% NaOMe/MeOH (Aldrich) was added over 2 hoursat rate to maintain a temperature of approximately 0° C. During theaddition a white precipitant, (NaCl) formed. The resultant was stirredan additional hour at 0° C. and then allowed to warm to room temperatureand stirred overnight. The precipitant was removed by filtration and thefiltrate was stripped of solvent yielding 20.33 g white gel. This gelwas slurried in 200 ml CH₂Cl₂ for 1 hour. The resultant was filtered,and the filtrate stripped of solvent yielding 9.47 g tan oil.

¹H & ¹³C-NMR'S showed a mixture of desired product, VSMS, and methyl2-methoxyethane-1-sulfonate in a 3:0.6 ratio, 79.8% product by weight.The H-NMR also shows and acid peak at ˜10 ppm. A test of 0.05 g tan oilin 1 ml water showed a pH of approximately 1 by litmus.

8.8 g of tan oil was dissolved in 100 ml CH₂Cl₂ and stirred over 5 gsodium bicarbonate. The resultant was filtered, and the filtratestripped of solvent yielding 8.02 g light yellow clear oil. A test of0.05 g of the yellow clear oil in 1 mL water showed a pH ofapproximately 6-7 by litmus. Ratio of VSME to methyl 2-methoxyethane-1-1sulfonate was the same, yielding 79.8% active.

Example 15 Synthesis of Sodium Vinyl Benzyl Sulfonate

A magnetically stirred dry 250 ml 3 neck round bottom flask equippedwith a heating mantel, addition funnel and reflux condenser was chargedwith 9.5 g of sodium sulfite (75.5 mmol) and 100 ml water. The resultantsolution was heated to 100° C. under nitrogen. Next, 4-vinylbenzylchloride (9.6 g, 62.9 mmol) in 15 ml acetone was added over 30 minutes.The resultant was refluxed 12 hours, cooled to room temperature andallowed to stand overnight with no resulting precipitant. Next, underrapid stirring, 100 ml acetone was added resulting in a lower paste-likelayer. The water/acetone supernatant was decanted. The paste was rinsedwith 25 mL of fresh acetone which was then decanted. The paste was driedovernight under vacuum, 14 torr, and room temperature to yield 8.5 gsolids. This dried layer was shown to be primarily homopolymer by¹H-NMR. The water/acetone decanted layers were evaporated toapproximately 75 ml yielding a white ppt. The ppt was collected byfiltration, rinsed 2×25 ml acetone and dried overnight under vacuum, 14torr, and room temperature to yield 2.14 g solids.

The ¹H-NMR of this second precipitant was consistent with monomerproduct at close to 100% activity.

Example 16 Co-Polymerization of Vinyl Phosphonic Acid (VPA) and SodiumVinyl Sulfonate (SYS)

VPA (2.0 g, 18.5 mmoles) and SVS (25% aqueous solution, 7.9 g, 15.2mmoles), initial molar ratio of SVS to VP A of 45 to 55, were charged ina round bottom flask. The flask was purged with nitrogen for 15 minutesand heated to 90° C. Two separate aqueous solutions containing2,2′-azobis(2-methylpropionamidine)dihydrochloride (AAPH, Aldrich, 25.8mg in 1.2 mL water, 0.3% molar basis to total monomers added) and1-Octanethiol (CTA, Aldrich 55.6 mg in 1.2 mL of water, 1.1% molar basisto total monomers added) were also prepared. These two solutions werethen added to the heated stirred flask containing the monomers every 30minutes over the course of 6 hours. After the final addition, theresulting solution was allowed to stir overnight at 90° C.

¹H-NMR & ³¹P-NMR were run on the crude reaction solutions. Typicalmonomer conversions of 95-99% were observed with a broad P polymer peakat ˜31 ppm from the phosphonate group. The crude reaction solutions werediluted to 1 wt % polymer in water and the pH adjusted to 6.

These solutions were dialyzed with 2K molecular weight cut off dialysismembranes against reverse osmosis water for 5-7 days.

The resultant solution was stripped of water under vacuum to yield whiteto cream color solids which was further dried in a vacuum oven overnightto yield 2.74 g of solid.

The phosphonate content in the polymers were determined by preparing anNMR sample with purified polymer & trimethyl phosphate (TMP) in D₂O. The¹H & ³¹P-NMR's were run from which the phosphonate content wascalculated from the H and P peaks of the internal standard (TMP)relative to the polymer peaks and water. Based on this analysis, thepolymer contained 55.7 mol % repeat units resulting from SVS and 44.3mol % repeat units resulting from VP A. The water content was calculatedto 9.6% on a weight basis. The total recovery of monomers in the postdialysis polymer was calculated to be 57% on a molar basis.

Example 17 Co-Polymerizations of Vinyl Phosphonic Acid and Sodium VinylSulfonate (SVS) The procedure of Example 16 was repeated for differentstarting ratios of VS A and VP A. The resulting polymer compositionsfrom different starting ratios and total yield, including Example 16 areshown in the Table 1 below. A Wyatt Gel Permeation Chromatography (GPC)system, using a Polymer Standards Service (PSS) MCX 1000A column andboth a Wyatt HELEOS II light scattering detector and a Wyatt OptilabDifferential refractive index detector, was used for calculation ofpolymer molecular weight using the internal Wyatt Astra 6 software.

TABLE 1 % Total % Total Total Monomer Monomer % AAPH % CTA % Sulfonate %Phosphonate Molar Mn Mw SVS Loaded VPA Loaded Loaded Loaded in Polymerin Polymer Yield (kDa) (kDa) 75.0% 25.0% 0.3% 1.0% 80% 20% 85% 5.4 7.970.0% 30.0% 0.3% 1.1% 69% 31% 66% 4.2 5.9 50.0% 50.0% 0.3% 1.0% 57% 43%73% — — 45.1% 54.9% 0.3% 1.1% 56% 44% 57% 3.4 4.5 40.0% 60.0% 0.3% 1.0%44% 56% 64% 4.2 5.3 20.0% 80.0% 0.3% 1.0% 34% 66% 58% — —

Example 18 Co-Polymerization of Vinyl Phosphonic Acid (VPA) and AcrylicAcid (AA)

The procedure in Example X was repeated using an initial charge of 19mmol of VPA in 1.5 mL of water. Acrylic acid, 28.5 mmol in 1.6 mL ofwater was added (0.3 mL) along with the 0.1 mL of AAPH and CTA every 30minutes. An additional 3 mL of water was added half way through theadditions. The final polymer collected was 2.87 g after dialysis and wasfound to be 30% phosphonate and 70% acrylate.

Example 19 Co-Polymerization of Vinyl Phosphono-monoPhosphate (VPP) andSodium Vinyl Sulfonate (SVS)

VPP (Example 1, 2.05 g active, 8.87 mmoles) and SVS (25% aqueoussolution, 3.77 g, 7.25 mmoles), initial molar ratio of SVS to VPP of 45to 55, were charged in a round bottom flask, and the headspace of theflask purged with flowing nitrogen for 15 minutes. The flask was sealedand heated to 60° C. at which time Ammonium Persulfate (APS, Aldrich,183 mg, 5% relative to total monomers) was added in 0.50 ml water. Theresultant was stirred 24 hrs at 60° C.

¹H-NMR & ³¹P-NMR were run on the crude reaction solutions. Typicalmonomer conversions of 95-99% were observed with broad P polymer peaksat ˜18 to 23 ppm from the phosphonate group and −6 to −10 from thephosphate bound to the phosphonate group.

The crude reaction solutions were diluted to 1 wt % polymer in water andthe pH adjusted to 8.5. These solutions were dialyzed with 2K molecularweight cut off dialysis membranes against reverse osmosis water for 5-7days.

Water was removed from the product by freeze drying yielding 2.22 gwhite solid.

The phosphonate content in the polymers were determined by preparing anNMR sample with purified polymer & trimethyl phosphate (TMP) in D₂O. The¹H & ³¹P-NMR's were run from which the phosphonate content wascalculated from the H and P peaks of the internal standard relative(TMP) relative to the polymer peaks and water. The P-NMR shows broadphosphono-phosphate peaks at ˜18 to 23 ppm and −6 to −10 ppm inapproximately 1:1 ratio and also a phosphonate peak at 26-28 ppm. Basedon the ³¹P-NMR areas at 18-23 and 26-28 ppm, thephosphono-phosphate:phosphonate ratio is 94.9:5.1. Based on thisanalysis, the polymer contained 56 mol % repeat units resulting fromSVS, 42 mol % repeat units resulting from VPP and 2 mol % repeat unitsresulting from VP A. The water content was calculated to 23% on a weightbasis. The total recovery of monomers in the post dialysis polymer wascalculated to be 65% on a molar basis

Example 20 Co-Polymerizations of Vinyl Phosphono-monoPhosphate (VPP) andSodium Vinyl Sulfonate (SVS)

The procedure of Example 19 was repeated for different starting ratiosof VS A and VPP. The resulting polymer compositions from differentstarting ratios and total yield, including Example 19 are shown in Table2 below.

TABLE 2 % Total % Total % Phosphono- Total Monomer Monomer % APS %Sulfonate Phosphate % Phosphonate Molar Mn Mw SVS Loaded VPP LoadedLoaded in Polymer in Polymer in Polymer Yield (kDa) (kDa) 74.9% 25.1%5.0% 81% 15% 4% 75% — — 75.0% 25.0% 5.0% 79% 20% 1% 79% — — 65.0% 35.0%5.0% 67% 30% 3% 55% — — 56.0% 44.0% 5.0% 62% 35% 3% 63% — — 55.2% 44.8%5.5% 66% 30% 3% 77% — — 50.0% 50.0% 5.2% 59% 40% 2% 65% 2.8 5.5 45.0%55.0% 5.0% 56% 42% 2% 58% — —

Example 21 Co-Polymerization of Methyl-Vinyl Phosphono-monoPhosphate(MVPP) and Sodium Vinyl Sulfonate (SVS)

The procedure of Example 19 was repeated using MVPP (Example 2) in placeof VPP and a ratio MVS to MVPP of 55 to 45, respectively, with thefollowing changes.

At 24 hours of run time, the MVPP monomer conversion via NMR was around75%, so an additional 3 mole % APS in water was added and the reactionallowed to stir for an additional 24 hours at 60° C. At this point, theMVPP monomer conversion was around 95%.

Dialysis and freeze drying were conducted as in Example 19.

Based on this NMR analysis, the polymer contained 62 mol % repeat unitsresulting from SVS, 35 mol % repeat units resulting from MVPP and 3 mol% repeat units resulting from methyl vinyl phosphonic acid. The watercontent was calculated to 10.3% on a weight basis. The total recovery ofmonomers in the post dialysis polymer was calculated to be 65% on amolar basis

Example 22 Homopolymerization of Vinyl Phosphono-monoPhosphate

VPP (Example 1, 16.4 mmoles) water, 6 mL, and sodium bicarbonate (0.69g, 8.2 mmoles) were charged in a 25 mL round bottom flask which was thenpurged with nitrogen for 15 minutes. Ammonium Persulfate (APS, 186.6 mg)was dissolved in 0.50 mL water and added to the mixture. The resultingsolution was allowed to stir 6 hours at 60° C. At this time, NMR showed25% polymerization monomer. An additional 186.6 mg of APS in 0.50 mL ofwater was added. The resultant was allowed to stir for a total of 24hours at 60° C. NMR showed no remaining monomer. The crude reactionsolution was diluted with 500 mL in water with a resulting pH of 8.7.This solution was dialyzed with 2K molecular weight cut off dialysismembranes against reverse osmosis water with an adjusted pH of 8.5.

The resultant solution was stripped of water under vacuum to yield whiteto cream color solids which was further dried in a vacuum oven overnightto yield 2.8 g of solid. P-NMR showed only VPP with no VP A. Theresultant was 91% polymer on a weight basis with the remaining water andimpurities. The total recovery of monomers in the post dialysis polymerwas calculated to be 58% on a molar basis.

Example 23 Co-Polymerization of Vinyl Phosphono-monoPhosphate (VPP) andSodium 2-Acrylamido-2-Methyl Propane Sulfonic Acid (AMPS)

VPP (Example 1, 6.55 mmoles) and water 2 mL were charged in a roundbottom flask, and the headspace of the flask purged with flowingnitrogen for 15 minutes. The flask was sealed and heated to 60° C. for15 minutes to yield a homogenous solution. Ammonium Persulfate (APS,149.3 mg) was dissolved in 1.2 g water. Every 30 minutes, 0.1 mL of theAPS solution and 0.206 mL of AMPS (3 g of 50% solution, 6.55 mmoles) wasadded to the reaction over a total of 6 hours. The resultant was stirred24 hrs at 60° C.

The crude reaction solution was diluted with 250 mL of water anddialyzed with 2K molecular weight cut off dialysis membranes againstreverse osmosis water for 6 days.

Water was removed from the product by freeze drying yielding 2.66 gwhite solid.

The phosphonate content in the polymers were determined by preparing anNMR sample with purified polymer & trimethyl phosphate (TMP) in D₂O. The¹H & ³¹P-NMR's were run from which the phosphonate content wascalculated from the H and P peaks of the internal standard relative(TMP) relative to the polymer peaks and water. The P-NMR shows broadphosphono-phosphate peaks at ˜18 to 23 ppm and −6 to −10 ppm inapproximately 1:1 ratio and also a phosphonate peak at 26-28 ppm. Basedon the ³¹ P-NMR areas at 18-23 and 26-28 ppm, thephosphono-phosphate:phosphonate ratio is 98:2. Based on this analysis,the polymer contained 64.2 mol % repeat units resulting from AMPS, 35.1mol % repeat units resulting from VPP and 0.7 mol % repeat unitsresulting from VP A. The water content was calculated to 13.3% on aweight basis.

Example 24 Co-Polymerization of Vinyl Phosphono-monoPhosphate (VPP) and3-Sulfopropyl Acrylate Potassium Salt (SPA)

The procedure of example 23 was followed with the substitution of SPA(Aldrich) for AMPS. Freeze drying of product yielded 2.04 g white solid.

Based on NMR analysis, the polymer contained 62 mol % repeat unitsresulting from SPA, 36 mol % repeat units resulting from VPP and 2 mol %repeat units resulting from VP A. The water content was calculated to15.5% on a weight basis.

Example 25 Co-Polymerization of VPP with Acrylamide

VPP (Example 1, 9.9 mmoles) and water, 3 mL, were charged in a roundbottom flask, and the headspace of the flask purged with flowingnitrogen for 15 minutes. The flask was sealed and heated to 60° C. for15 minutes to yield a homogenous solution. Ammonium Persulfate (APS,225.9 mg) was dissolved in 1.2 g water. Acrylamide (Aldrich, 9.9 mmoles)was dissolved in 1.5 g water Every 30 minutes, 0.1 mL of the APSsolution and 0.125 mL of the acrylamide solution was added to thereaction over a total of 6 hours. The resultant was stirred 24 hrs at60° C. Progress was monitored by NMR.

The crude reaction solution was diluted with 250 mL of water anddialyzed with 2K molecular weight cut off dialysis membranes againstreverse osmosis water for 5 days.

Water was removed from the product by freeze drying yielding 2.85 gwhite solid.

The phosphonate content in the polymers were determined by preparing anNMR sample with purified polymer & trimethyl phosphate (TMP) in D₂O. The¹H & ³¹P-NMR's were run from which the phosphonate content wascalculated from the H and P peaks of the internal standard relative(TMP) relative to the polymer peaks and water. The P-NMR shows broadphosphono-phosphonate peaks at ˜18 to 23 ppm and −6 to −10 ppm inapproximately 1:1 ratio. No phosphonate peak was observed at ˜26-28 ppm.Based on this analysis, the polymer contained 53 mol % repeat unitsresulting from acrylamide, 47 mol % repeat units resulting from VPP. Thewater content was calculated to 16% on a weight basis.

Example 26 Co-Polymerization of VPP with VSMS

VPP (Example 1, 7.67 mmoles), bicarbonate (Aldrich 11.5 mmol) and water,5 mL, were charged in a round bottom flask, and the headspace of theflask purged with flowing nitrogen for 15 minutes. The flask was sealedand heated to 60° C. for 15 minutes to yield a homogeneous solution.Ammonium Persulfate (APS, 174.9 mg) was dissolved in 1.2 g water. Every15 minutes, 0.1 mL of the APS solution and 0.084 mL of VSME (Vinylsulfonate methyl ester (Example 14, 79.8% Active, 7.67 mmole total) wasadded to the reaction over a total of 3 hours. The resultant was stirredan additional 3 hrs at 60° C. The crude reaction solution was dilutedwith 250 mL of water and dialyzed with 2K molecular weight cut offdialysis membranes against reverse osmosis water at a pH of 8.5 for 5days.

Water was removed from the product by freeze drying yielding 2.05 gwhite solid.

The phosphonate content in the polymers were determined by preparing anNMR sample with purified polymer & trimethyl phosphate (TMP) in D₂O. The¹H & ³¹P-NMR's were run from which the phosphonate content wascalculated from the H and P peaks of the internal standard relative(TMP) relative to the polymer peaks and water. The P-NMR shows broadphosphono-phosphate peaks at 18 to 23 ppm and −4 to −10 ppm inapproximately 1:1.1 ratio but no phosphonate peak at 26-28 ppm. Thetotal phosphorous content was 40.8%. The methyl proton from MSME wasvisible in the ¹H NMR and allowed quantification of VSME hydrolysis.Based on the total analysis, the polymer contained 39 mol % repeat unitsresulting from VSME, 20 mole % VSA, and 41 mol % repeat units resultingfrom VPP. The resultant was 73% polymer on a weight basis with theremaining water and impurities.

Example 27 Co-Polymerization of (Phosphono-monoPhosphate Ethyl) (Butyl)Acrylamide with AMPS

(Phosphono-monoPhosphate Ethyl) (Butyl) Acrylamide (Example 4, 21.6mmoles) and AMPS (23.6 mmoles) were polymerized as in Example 23. Thecrude reaction solutions were dialyzed with 1K molecular weight cut offdialysis membranes against reverse osmosis water overnight, followed by2 hours dilation against 0.5 M NaCl and then 1 hr against 0.05M NaCl.After freeze drying, 11.5 grams of material was collected. NMR as inother examples found the polymer to be approximately 67 mol % repeatunits resulting from AMPS, and 33% from (Phosphono-monoPhosphate Ethyl)(Butyl) Acrylamide. The solid containing around 16% water, by weight andwas 55% polymer by weight.

Example 28 Co-Polymerization of VPP with VPA

VPA (1.2 g, 11.1 mmoles) and water 6 mL were charged in a 25 mL roundbottom flask. Sodium bicarbonate (2.8 g, 33.3 mmoles) was added over 60minutes and the flask was then purged with nitrogen left to stir overnight at room temperature. VPP (Example 1, 11.1 mmoles) was added andthe solution purged with nitrogen and heated to 60° C. yielding a turbidsolution. Ammonium Persulfate (APS, 253.5 mg) was dissolved in 0.75 mLwater and added to the mixture. The resulting solution was allowed tostir 6 hours at 60° C. At this time, NMR showed 40% polymerization ofall monomers. An additional 253.3 mg of APS in 0.75 mL of water wasadded. The resultant was allowed to stir for a total of 24 hours at 60°C. NMR showed 10% remaining monomer.

The crude reaction solution was diluted with 500 mL in water with aresulting pH of 8.7. This solution was dialyzed with 2K molecular weightcut off dialysis membranes against reverse osmosis water with anadjusted pH of 8.5.

The resultant solution was stripped of water under vacuum to yield whiteto cream color solids which was further dried in a vacuum oven overnightto yield 2.66 g of solid. P-NMR showed the ratio of VPP:VPA to be 61:39in the polymer. The resultant was 88% polymer on a weight basis.

Example 29 Co-Polymerization of VPP with Methyl Acrylate

VPP (Example 1, 9.9 mmoles) and water, 4 mL, were charged in a roundbottom flask, and the headspace of the flask purged with flowingnitrogen for 15 minutes. The flask was sealed and heated to 60° C. for15 minutes to yield a homogeneous solution. Ammonium Persulfate (APS,225.7 mg) was dissolved in 1.2 g water. Every 30 minutes, 0.1 mL of theAPS solution and 0.073 mL Methyl Acrylate (Aldrich, 9.9 mmoles, 0.88 mLtotal) solution was added to the reaction over a total of 6 hours. At 3hours a milky white color began to form. The resultant was stirred 24hours at 60° C. yielding a milky white solution. Progress was monitoredby NMR and showed 20% remaining VPP at 24 hours and no remaining methylacrylate.

The reaction solution was added to 20 mL of additional water and 5 mL ofMeOH was then added over 5 minutes under rapid stirring. Resultant wasallowed to sit at room temperature for 10 minutes yielding a whiteprecipitate. The precipitate was filtered and the MeOH was removed fromthe filtrate.

The filtrate was diluted with 250 mL of water and dialyzed with 2Kmolecular weight cut off dialysis membranes against reverse osmosiswater for 5 days at a pH of approximately 6.5. Water was removed fromthe product by freeze drying yielding 1.4 g white solid.

The phosphonate content in the polymers were determined by preparing anNMR sample with purified polymer & trimethyl phosphate (TMP) in D₂O. The¹H & ³¹P-NMR's were run from which the phosphonate content wascalculated from the H and P peaks of the internal standard (TMP)relative to the polymer peaks and water. Analysis showed the resultingpolymer to be 29% methyl acrylate, 16% Acrylate, 50% VPP, and 5% vinylphosphonate. The resulting solid was 77% polymer on a weight basis.

Example 30 Co-Polymerization of (4-Vinylbenzyl) Phosphono-monoPhosphatewith SYS

(4-VinylBenzyl) Phosphono-monoPhosphate (VBPP, Example 5, 4.35 mmoles),bicarbonate (Aldrich 183 mg, 8.2 mmol) and SVS (Aldrich, 25% aqueoussolution, 8.1 mmoles), were charged in a round bottom flask, and theheadspace of the flask purged with flowing nitrogen for 15 minutes. Theflask was sealed and heated to 60° C. at which time a gas was evolved.Additional bicarbonate (total of 300 mg) was incrementally added untilno additional off gassing was observed. Ammonium Persulfate (APS,Aldrich, 284 mg, 10% relative to total monomers) was added in 0.5 mlwater. The resultant was stirred 24 hrs at 60° C.

¹H-NMR & ³¹P-NMR were run on the crude reaction solutions. The polymercomposition approximately 25/75 SVS/VBPP.

The crude reaction solution was diluted with 500 mL water and the pHadjusted to 8.5 with 1 N NaOH. This solution was dialyzed with 2Kmolecular weight cut off dialysis membranes against reverse osmosiswater for 6 days. Water was removed from the product by freeze dryingyielding 1.85 g white solid.

The phosphonate content in the polymers were determined by preparing anNMR sample with purified polymer & trimethyl phosphate (TMP) in D₂O. The¹H & ³¹P-NMR's were run from which the phosphonate content wascalculated from the H and P peaks of the internal standard (TMP)relative to the polymer peaks and water. The P-NMR shows broadphosphono-phosphate peaks at ˜13 to 15 ppm and −5 to −7 ppm inapproximately 1:1 ratio and also a phosphonate peak at ˜21-23 ppm. Basedon the ³¹P-NMR areas at 13-15 and 21-23 ppm, thephosphono-phosphate:phosphonate ratio is 93:7. Based on this analysis,the polymer contained 30 mol % repeat units resulting from SVS, 65 mol %repeat units resulting from VBPP and 5 mol % repeat units resulting from(4-VinylBenzyl)Phosphonate. The water content was calculated to 18% on aweight basis.

Example 31 Co-Polymerization of (Phosphono-monoPhosphateEthyl)-Acrylamide with SVS

SVS, (Aldrich, 25% aqueous solution, 4.73 mmoles), was charged in around bottom flask, and the headspace of the flask purged with flowingnitrogen for 15 minutes. The flask was sealed and heated to 60° C.Ammonium Persulfate (APS, Aldrich, 141 mg, 5% relative to totalmonomers) was added in 1.0 g water.Phosphono-monoPhosphate(Ethyl)-Acrylamide (Example 9, 4.95 mmoles) wasadded to 5.25 g water. To the flask with SVS, 0.1 mL APS solution and1.0 mL (Phosphono-monoPhosphate Ethyl)-Acrylamide was added every 20minutes for 3 hours. The resultant was stirred and additional 4 hours at60° C.

The crude reaction solution was diluted with 500 mL water and the pHadjusted to 8.5 with 1 N NaOH. This solution was dialyzed with 2Kmolecular weight cut off dialysis membranes against reverse osmosiswater for 6 days. Water was removed from the product by freeze dryingyielding 3.4 g tan solid. H-NMR & P-NMR were run on the crude reactionsolutions. The polymer composition approximately 62:36:2SVS:(Phosphono-monoPhosphate Ethyl)-Acrylamide: (PhosphonateEthyl)-Acrylamide

Example 32 Post Polymerization Modification of Co-Polymer of VPA and AA

The polymer from example 18 was esterified by refluxing 2.3 grams in 150mL of MeOH in a 250 mL 1 neck round bottom flask equipped with a heaterand magnetic stirring. After 1 hour of refluxing, a short pathdistillation head was added and approximately ⅓ of the MeOH was removed.This MeOH was then replace with fresh anhydrous MeOH a total of 4 times.This procedure yielded about 47% conversion to the methyl ester ofacrylic repeat units. Next, 2 drops of concentrated sulfuric acid wereadded, and the solution was refluxed for 48 hours. This procedureincreased the total methyl ester content to 83% by H NMR. In addition,around 9% of the phosphonate esters were converted to mono-methylphosphonate esters by P NMR.

A magnetically stirred dry 50 ml 1 neck round bottom flask was chargedwith the methyl ester containing polymer (0.5, 1.63 mmole P) and 15 mlDMF under nitrogen. The resulting mixture was stirred overnight at roomtemperature yielding a swelled ball of polymer. Next, tributylamine(0.78 mL, 2.0 equivalents relative to P monomer) was added and stirredovernight at room temperature yielding a homogeneous solution. CDI (330mg, 1.25 equivalents relative to P monomer) and 5 mL DMF were premixedand added to solution. The resulting mixture was stirred overnightyielding a homogeneous solution.

H₃PO₄ (479 mg, 3 equivalents), tributylamine (1.26 mL 3.5 equivalent)and 5 mL of DMF were mixed and sonicated then added to the polymercontaining solution. Resultant was stirred overnight at roomtemperature. Resulting solution was stripped of solvent under vacuum (9Torr) to a final temperature of approximately 60° C.

The resultant was dissolved in 50 ml of 1 N NaOH yielding a solution atpH 13.15 and stirred overnight. Resultant was stripped of water withflowing dry nitrogen to yield a white paste. The paste was dissolved in60 mL of MeOH over 1 hour and the resulting solid collected and dried to2.52 grams.

The crude solid was dissolved in water, pH adjusted to 9 and resultingsolution dialyzed as described in previous examples. 0.67 g of whitefluffy solid was collected after lyophilization. P NMR showed around 20%yield of phosphono-monophosphate groups from initial phosphonate groups.

Example 33 Co-Polymerization of (Phosphono-monoPhosphateEthyl)-Methacrylate with SYS

The procedure of example 31 was followed using 5.7 mmoles of SVS, and3.79 mmoles of (Phosphono-monoPhosphate Ethyl)-Methacrylate from Example7. After freeze drying, 1.5 g white solid was collected at 86% polymer,14% water/inactives. The polymer composition approximately 63:35:2SVS:(Phosphono-monoPhosphate Ethyl)-Methacrylate: (PhosphonateEthyl)-Methacrylate.

Example 34 Co-Polymerization of (PropylPhosphono-Monophosphate)-Methacrylate with SVS

The procedure of example 31 was followed using 3.7 mmoles of SVS, and3.5 mmoles of (Propyl Phosphono-monoPhosphate)-Methacrylate from Example8. After freeze drying, 1.84 g white solid was collected at 86% polymer,14% water/inactives. The polymer composition approximately 56:44SVS:(Propyl Phosphono-monoPhosphate)-Methacrylate.

Example 35 Post Polymerization Modification of Homopolymer of VPA

Poly(vinylphosphonic acid) (500 mg) was added to a 100 ml round bottomflask followed by methanol (20 ml). Tributylamine (1.1 mL) was added tothe mixture and stirred for 30 minutes and the mixture becamehomogeneous. Resulting solution was concentrated under vacuum followedby the addition of pyridine (10 mL) and removal under vacuum threetimes. Resulting solid was dissolved in 10 mL pyridine. Diphenylphosphoryl chloride (956 μL, 1 equivalent) was slowly added however, aprecipitate formed in the reaction mixture, so it was diluted withadditional pyridine (50 ml). After 1 hour mono(tributylamine) phosphatewas added (3.3 mL, 3 equivalents) and this was stirred overnight.Solvent was removed under vacuum and the resulting solid was dissolvedin water and dialyzed. After dialysis the water was removed via freezedrying to yield a sticky solid. PNMR analysis indicated 87.7% of thephosphonates had for an anhydride with an adjacent phosphonate, while12.3% were phosphono-monophosphate.

Example 36 Post Polymerization Modification of PolyMethyl-VinylPhosphonate

Following a similar procedure to Example 32 a magnetically stirred dryround bottom flask is charged with poly methyl-vinyl phosphonate, DMFand purged with nitrogen. Next, tributylamine (2.0 equivalents relativeto P monomer) is added and stirred overnight at room temperatureyielding a homogeneous solution. CDI (1.25 equivalents relative to Pmonomer) and DMF are premixed and added to solution which is stirredovernight. H₃PO₄ (3 equivalents), tributylamine (3.5 equivalent) and DMFare mixed and sonicated then added to the polymer containing solution.Resultant is stirred overnight at room temperature. Resulting solutionis stripped of solvent under vacuum (9 Torr) to a final temperature ofapproximately 60° C. to yield a phosphono-phosphate containing polymer.

Example 37 Post Polymerization Modification of Random PhosphonateContaining Polymer

Phosphonated polyethylene is synthesized by following the description ofAnbar (M. Anbar, G. A. St. John and A. C Scott, J Dent Res Vol 53, No 4,pp 867-878, 1974) or Schroeder and Sopchak (J, P. Schroeder and W. P.Sopchak, Journal of Polymer Science Volume 47 Issue 149 p 417 (1960)).Briefly 10 g polyethylene is reacted in a dry flask with 200 g of PCl₃at reflux until the polymer dissolves. Next dry oxygen is flowed throughthe dissolved solution. Resulting solution is distilled to reduce theoverall volume by half and is poured over ice chips to createphosphonated polyethylene. This phosphonated polyethylene is reactedfollowing the procedure of Example 36.

Example 38 Post Polymerization Modification ofPoly(Vinylbenzylphosphonic Acid) Containing Polymer

Poly(vinylbenzylphosphonic acid) is synthesized by polymerizing(4-VinylBenzyl) Phosphonic Acid using either heat in methanol asdescribed by Anbar et al. or by using an initiator such as ammoniumpersulfate at 5-10% loading relative to monomer. The resulting polymeris reacted following the procedure of Example 36.

Example 39 Synthesis of a Phosphono Phosphate Monomer and Polymer on aSide Chain

The procedure of Example 12 is followed substituting an ethylene glycoldimer, trimer, tetramer or polymer with a primary hydroxy group such asdiethyl (2-hydroxyethoxy)ethoxy)ethyl)phosphonate for dimethyl(2-hydroxyethylphosphonate. Ethyl phosphonate terminated ethylene glycolunits can be synthesized by following the procedure of Brunet et al(Ernesto Brunet, * Mari´ a Jose´ de la Mata, Hussein M. H. Alhendawi,Carlos Cerro, Marina Alonso, Olga Juanes, and Juan Carlos Rodi´guez-Ubis, Chem. Mater. 2005, 17, 1424-1433). Briefly, the desiredethylene glycol dimer, trimer, tetramer or polymer (1 equivalent) isadded over 2-4 days to a 90° C. mixture of Cs₂CO₃ (1.2 equivalents)diethylvinylphosphonic acid (12.5 equivalents). Purification isperformed by extracting with water dichloromethane followed by flashchromatography. Polymerization of the phosphono-phosphate containingmonomer is performed as described in Example 22 to yield a homopolymeror with co-monomers as described in Examples 19, 20, 23, 24, 25, or 26to yield co-polymers.

Example 40 Synthesis of a Phosphono Phosphate Polymer on a Side Chain byPost-Polymerization Modification

Ethoxylated polyvinyl alcohol is reacted as described in Example 38 tocreate a phosphonate terminated ethoxylated polyvinyl alcohol polymer.Ethoxylated polyvinyl alcohol is synthesized by reacting polyvinylalcohol in a sealed reactor at a temperature of 85-120° C. and apressure of 20-200 psig with a base catalyst such as methoxide or sodiumhydroxide and ethylene oxide added slowly over several hours. Thisphosphonate terminated polymer is reacted as described in Example 36 tocreate a phosphono-phosphate containing polymer where thephosphono-phosphate is attached to a side chain of the polymer bypost-polymerization modification.

Example 41 Co-Polymerization of Di-Methyl Vinyl Phosphonate (DMVP) withSYS

SVS (Aldrich, 25% aqueous solution, 11.0 mmoles) was charged in a roundbottom flask, and the headspace of the flask purged with flowingnitrogen for 15 minutes. The flask was sealed and heated to 60° C. for15 minutes. Ammonium Persulfate (APS, 225 mg) was added in 1.0 g water.Every 30 minutes, 0.1 mL of the APS solution and 0.1 mL of DMVP(Aldrich, 1.5 g, 1.3 mL, 11.0 mmoles) were added to the reaction over atotal of 6 hours. The resultant was stirred 24 hrs at 60° C.

The crude reaction solution was diluted with 250 mL of water anddialyzed with 2K molecular weight cut off dialysis membranes againstreverse osmosis water for 4 days. The initial pH of the dialysis waterwas 5.8 but dropped to 2.5.

Water was removed from the product by freeze drying yielding 2.4 g whitesolid.

Based on NMR analysis the polymer contained 56.9 mol % repeat unitsresulting from SVS, 43.1 mol % DMVP. The water content was calculated to10.4% on a weight basis.

Example 42 Co-Polymerization of Example 23 Co-Polymerization of (EthylPhosphono-monoPhosphate)-Vinyl Ether and (AMPS)

(Ethyl Phosphono-monoPhosphate)-Vinyl Ether (Example 11, 4.7 mmoles),water 5 mL, and AMPS (4 g of 50% solution, 8.7 mmoles) were charged in around bottom flask, and the headspace of the flask purged with flowingnitrogen for 15 minutes. The flask was sealed and heated to 60° C. for15 minutes to yield a homogenous solution. Ammonium Persulfate (APS, 306mg) was dissolved in 1.1 g water. Every 30 minutes, 0.1 mL of the APSsolution was added to the reaction over a total of 4 hours. Theresultant was stirred 4 hours at 60° C.

The crude reaction solution was diluted with 750 mL of water anddialyzed with 2K molecular weight cut off dialysis membranes againstreverse osmosis water for 8 days.

Water was removed from the product by freeze drying yielding 2.12 g tansolid.

Based on NMR analysis, the polymer contained 90.8 mol % repeat unitsresulting from AMPS, 9.2 mol % repeat units resulting from (EthylPhosphono-monoPhosphate)-Vinyl Ether. The solid was found to contain 77%water by weight.

General Chemical Scheme for Examples 43-49—Synthesis of VinylPhosphono-monoPhosphate (VPP) or [Vinylphosphonic Phosphoric Anhydride]and Other Extended Vinyl Phosphono-Phosphates (eVPP) by Removal of Water

The following chemical scheme shows general reaction scheme in Examples43-49 used to form the primary desired products, VPP and VPPP, alongwith some of the other products observed in some but not all of thefollowing experiments. Please refer to individual examples for finalidentified product distributions

Example 43—Synthesis of VPP and eVPP by Evaporation Using a Sweep Gaswith 3 Equivalents of PA

A 50 mL 3 neck round bottom flask, equipped with a magnetic stirrer anda short path distillation head in the middle neck, was charged with 1gram of vinyl phosphonic acid (VPA) and 2.72 g (3 equivalents) of 99%phosphoric acid (PA). One side neck was stoppered, and nitrogen wasswept through the other side neck and out through the distillation head.The flask was placed in oil bath heated to 105° C. and stirred at thattemperature for 27 hours. Samples (1 drop) were removed at desired timepoints, dissolved in 1 mL D7-DMF with 0.25 mL tributyl amine, andevaluated by P-NMR. The final product was found to contain VPA,Vinyl-Phosphono-monoPhosphate (VPP), Vinyl-Phosphono-Pyrophosphate(VPPP), Vinyl-Phosphonic Acid Anhydride (VPPV), Phosphoric acid (PA),Pyrophosphoric Acid (PP) & Tri-Phosphoric Acid (PPP). Speciesidentification was confirmed using LCMS. In addition, H-NMR was run onthe final 27 hour sample from which it was determined that nopolymerization occurred during the reaction.

Final molar distributions of all vinyl containing species in the melt at27 hours was found to be 43% VPA, 38% VPP, 9% VPPP, and 10% VPPV.

Example 44—Synthesis of VPP and eVPP by Evaporation Using Vacuum and aSweep Gas with 3 Equivalents of PA

The procedure of example 43 was followed with the following changes. Theshort path distillation head was connected to a Buchi vacuum pump ratherthan venting to atmosphere. The round bottom flask was evacuated to50-60 Torr for the duration of the experiment with constant flow ofnitrogen from one side neck. Sampling at 32 and 48 hours showed littlechange between the time points with a vinyl containing distribution of31-32% VPA, 40-41% VPP, 14% VPPP, and 13-14% VPPV. Signals correspondingto VPPPV were also observed in P-NMR but were not quantified do tooverlap with other peaks.

Example 45—Synthesis of VPP and eVPP by Evaporation Using Vacuum and aSweep Gas with 6 Equivalents of PA

The procedure of example 44 was followed with 6 equivalents of PArelative to VPA. The distribution of vinyl containing species at 72hours was 31% VPA, 40% VPP, 21% VPPP, and 8% VPPV. Signals correspondingto VPPPV were also observed in P-NMR but were not quantified do tooverlap with other peaks.

Example 46—Synthesis of VPP and eVPP by Reaction with PhosphorousAnhydride (P₂O₅, Phosphorous Pentoxide)

To a magnetically stirred 20 mL scintillation vial was added 2.24 g of85 weight % phosphoric acid in water, 1.01 g 90% vinyl phosphonic acidand 2.5 phosphorous pentoxide (in that order). The molar ratio of vinylphosphonate to total phosphate (calculated as the sum of the moles ofphosphate plus twice the moles of P₂O) as 6. The vial was heated to 175°C. and sampled for P NMR at 1 hour using the procedure of example X. Themolar composition of identified vinyl containing species was 34% VPA,41% VPP, 19% VPPP and 5% VPPV. Additional vinyl peaks were visible in PNMR that likely correspond to larger species including VPPPP, andVPPPPP. LCMS confirmed the existence of higher orderphosphono-phosphates with peaks for VPP, VPPP, VPPPP, VPPPPP, VPPPPPP,and VPPPPPPP all visible in negative ion mode.

Example 47—Scale Up and Purification of Example 44

The procedure of example 49 was followed with a 5-fold increase in totalmaterials. Sampling at 32 hours showed a distribution of vinylcontaining species of 35% VPA, 37% VPP, 12% VPPP, 12% VPPV and 4% VPPPV.

After cooling, the bulk of the crude reaction mixture was dissolved in40 ml anhydrous DMF. The dissolved solution was added to a solution of28.1 g triethyl amine (1.5 equivalents based on total starting acid) in100 mL of anhydrous DMF with rapid stirring over 5 min. The P-NMR wasrun on the resultant solution and was consistent with distributions fromthe crude reaction mixture.

The resultant solution was stripped of DMF at 70° C. & 25 Torr yielding38.4 g viscous yellow oil. This was dissolved in 100 mL H₂O yielding asolution with a pH of 2.5, which was adjusted to 11.0 with 110 g 10%NaOH yielding a clear solution. The P-NMR was run on the resultantsolution which showed a consistent product distribution as previoussamples, but with an approximate 20% reduction in VPPV. Upon standing atroom temperature for 1 hour, a white precipitant formed which wascollected by filtration, dried overnight in ambient air to 4.65 g Thisprecipitant was found to be about 90% pyrophosphate, with 4% phosphateand less than 3% each of VPA, VPP and PPP. The filtrate was stripped ofsolvent yielding 49.4 g clear viscous oil. The pH of the resultant oilwas checked by litmus and found to be around 7. This was brought up toapproximately 125 g with additional water yielding a pH of 7.5 which wasadjusted to 11.0 with 15.2 g 1N NaOH. To this pH 11 solution was added250 ml MeOH with rapid stirring over 30 min. at room temperature. Awhite precipitant formed over the course of one hour. This precipitantwas collected by filtration, rinsed one time with 50 mL 2:3 H2O:MeOH anddried under ambient air overnight to 17.9 g. This precipitant was foundto be approximately 43% pyrophosphate, 39% phosphoric acid, 10% PPP, 3%VPP and 4% VPPP. The MeOH water solution was concentrated under flowingnitrogen overnight at room temperature to yield 31.1 g of viscous oil.The oil was found to have a molar phosphorous distribution ofapproximately 33% VPA, 33% VPP, 8% VPPP, 11% PA, 10% VPPV and 3% VPPPV.The oil was also found to have residual water and DMF.

To the oil, 300 ml MeOH was added over 1 hr at room temperature yieldinga white precipitant which was collected by filtration, rinsed 1×50 mLMeOH and dried under vacuum at room temperature for 2 hrs to yield 4.3 gwhite powder. The powder was found to have a molar phosphorousdistribution of 49% VPP, 26% PA, 6% PP, 15% VPPP and 3% VPA. The MeOHsolution was concentrated under flowing nitrogen at room temperature 7.0g white paste. The composition of the white paste was found to beapproximately 73% VPA, 23% VPP and 5% VPPPV.

Example 48—Polymerization to Create VPPP Containing Polymer

The white powder from example 47 containing 49% VPP, 26% PA, 6% PP, 15%VPPP and 3% VPA, was polymerized following the procedure of Example 19and 20 using a 50/50 mixture (total molar vinyl basis) of the white VPPPcontaining powder (8.6 mmol vinyl groups) and SVS (8.6 mmol vinylgroups). After dialysis and freeze drying, 3.6 g of polymer wascollected and found to contain 57% monomers based on SVS, and 43% basedon phosphonates. The phosphonate distribution was 3% from VPA, 78% fromVPP and 18% from VPPP. The polymer was 78% active on a weight basis with22% impurities/water.

Example 49—Synthesis of VPP and eVPP by Reaction with Phosphoric Acidand Urea

For all samples in the example, the following general procedure wasfollowed:A scintillation vial was charged with VPA, 85% or 99% H₃PO₄, urea &water as noted in the Table 1 below. The resultant was stirred at 60° C.for approximately 15 minutes until a homogenous solution was obtained.The resultant solution was transferred hot into an 800 mL beaker. Thiswas placed in a programmable lab oven with circulating air flow andexterior ventilation. All samples were heated as follows:1) Ramped from room temperature to 110° C. over 15 minutes.2) Hold at 110° C. 3 hours.3) Ramped from 110° C. to 150° C. over 15 minutes.4) Hold at 150° C. for either 15 or 60 minutes as noted in table below.5) Cooled to room temperature and allow to stand overnight.P-NMR was run on the crude reaction products (˜50 mg reaction product in1 mL D₂O with 5 drops 30% NaOD). The products were found to contain VPA,vinyl-phosphono-phosphate (VPPA), vinyl-phosphono-pyrophosphate (VPPPA),vinylphosphonic anhydride (SM-An), phosphoric acid (PA), pyrophosphoricacid & tri-phosphoric acid (PPP). Areas from P-NMR are shown in Table 3below. H-NMR's were also run on the reaction products to check forpolymerization of the VPA during the heating. No polymer was observed.

TABLE 3 % Areas from P NMR Sample Prep & Rx Conditions Rx VPPA + g g g gEquiv Equiv Equiv Time # VPA VPPA VPPPA SM-An VPPPA VPA H2O H3PO4/% UreaVPA H3PO4 Urea 150 C. 1 46.9 22.7 5.0 25.4 27.7 0.5 1.5 0.58 g 85% 0.331 1.1 1.2 15 min 1 48.9 29.5 7.1 14.4 36.6 0.5 1.5 1.16 g 85% 0.66 1 2.22.4 15 min 3 33.4 38.5 13.4 14.8 51.8 0.5 1.5 1.75 g 85% 1 1 3.3 3.6 15min 4 36.4 40.2 15.7 7.6 56.0 0.5 1.5 3.48 g 85% 2 1 6.6 7.2 15 min 5100.0 0.0 0.0 0.0 0.0 0.5 1.5 3.48 g 85% 0 1 6.6 0 15 min 6 33.1 38.119.2 9.6 57.3 0.5 0 2.95 g 99% 2 1 6.6 7.2 15 min 7 48.5 34.3 10.5 6.744.8 0.5 1.5 3.48 g 85% 2 1 6.6 7.2 60 min 8 45.8 36.2 11.1 6.9 47.3 0.50 3.48 g 85% 2 1 6.6 7.2 60 min 9 54.7 29.5 7.4 8.4 36.9 0.5 0 1.75 g85% 1 1 3.3 3.6 60 min 10 54.1 32.1 8.3 5.5 40.4 0.5 0 2.95 g 99% 2 16.6 7.2 60 min 11 32.1 38.1 21.9 7.8 60.1 0.5 0 3.48 g 85% 2 1 6.6 7.215 min 12 41.7 32.4 14.0 11.9 46.4 0.5 0 1.75 g 85% 1 1 3.3 3.6 15 min13 33.0 36.5 22.0 8.5 58.5 0.5 0 2.95 g 99% 2 1 6.6 7.2 15 min 14 40.229.6 17.0 13.2 46.6 0.5 0 3.48 g 85% 4 1 6.6 14.4 15 min 15 42.7 25.722.7 8.9 48.4 0.5 0 1.75 g 85% 2 1 3.3 7.2 15 min

Example 50—Synthesis of Polymer Containing VPP and eVPP by Reaction ofPolymer with Phosphoric Acid and Urea

Dimethyl vinyl phosphonate, DMVP (10.6 g, 77.9 mmoles) and sodium vinylsulfonate solution, SVS (25% aqueous solution, 40.5 g, 77.9 mmoles),were charged in a 100 mL round bottom flask. The flask was purged withnitrogen for 15 minutes and heated to 60° C. Ammonium persulfate, APS,888 mg, 2.55% of total monomer, was brought up in 4 g of water anddegassed with nitrogen for 5 minutes. The APS solution was added to thesolution containing DMVP and SVS and resultant solution was allowed tostir for 24 hours under nitrogen at 60° C.

¹-NMR & ³¹P-NMR were run on the crude reaction solution, and a monomerconversion of around 99% was observed with a broad P polymer peak at ˜37ppm from the phosphonate group.

The crude reaction solution was diluted to 10 wt % polymer in water with207 g of water. To this was added 300 mL of acetone over 30 minutesunder continuous stirring at room temperature to yield a turbidsolution. After standing in a separatory funnel for 30 minutes a lowerviscous polymer rich syrup and upper fluid organic layer were formed.The lower layer was collected, solvent evaporated under nitrogenovernight followed by vacuum, 2 hours at 1 Torr to yield 15.3 grams of atacky tan solid. ¹H-NMR & ³¹P-NMR were run on this solid with aninternal standard, trimethyl phosphate, to show a 50:50 ratio ofDMVP:SVS derived groups.

The tacky tan solid was mixed with 30 grams of water and 45 grams ofconcentrated HCl (≈37%) to yield a milky white solution. This mixturewas refluxed for 48 hours to yield a transparent solution with a slightbrown color. The water and HCl were stripped from the solution on aroto-vap operating at 60° C. and 20 torr to a total volume of ≈20 mL.100 additional mL of water was added to this remaining fraction and thestripping was repeated, then 200 mL of water was added, the sample wasfrozen and lyophilized to yield 11.8 g of tan solid. ³¹P-NMR showed ashift in the polymer beak from ≈37 to ≈32 ppm, while the ¹H-NMR showedthe disappearance of the peak polymer peak at 3.8 ppm that correspondedto the methyl ester peak. Analysis with an internal standard indicated aratio of P containing groups to sulfur containing groups ofapproximately 47 to 53, and a weight activity of 82.4%.

A 100 mL beaker was charged with 4.85 grams of 85% phosphoric acid and2.77 grams of urea and heated to 60° C. for 15 minutes then cooled toroom temperature to yield a clear solution. 5 grams of 82.4% activepolymer with a calculated ratio of P to S of 47 to 53 was dissolved in15 mL of water and this was added to the phosphoric acid/urea mixture inthe 100 mL beaker. This was placed in a programmable lab oven withcirculating air flow and exterior ventilation and heated as follows:

1) Ramped from room temperature to 110° C. over 15 minutes.2) Hold at 110° C. 3 hours.3) Ramped from 110° C. to 150° C. over 15 minutes.4) Hold at 150° C. for 15 minutes.5) Cooled to room temperature and allow to stand overnight.

11.4 grams of spongy white product was collected. P-NMR was run on thecrude reaction products (˜150 mg reaction product in 1 mL D₂O with 2drops 30% NaOD). P-NMR demonstrated a broad peak at ˜5 ppm correspondingto a phosphono-phosphate group on a polymer chain. A portion of thispeak is overlapped by pyrophosphate making quantification difficult.

The bulk of the crude, 11.4 g, was dissolved in 50 mL of water, chargedto a round bottom flask under stirring and 50 mL of methanol added over30 minutes to yield a turbid solution. Upon standing in a separatoryfunnel for 30 minutes, a lower viscous polymer rich syrup layer resultedwhich was separated (9.5 g). The ratio of polymer to phosphate topyrophosphate was evaluated by P-NMR and found to be 161 to 43 to 113.

The precipitation was repeated on the above 9.5 grams of syrup using 50mL of water and 50 mL of methanol. 2.13 g syrup resulted. P-NMR showedthe polymer to phosphate to pyro ratio to be 158 to 3 to 18.

The resultant syrup was brought up to 250 mL of reverse osmosis (RO)water further purified by dialysis in a Thermo Scientific Slide-A-Lyzerdialysis flask (2K MWCO) against RO water (pH adjusted to 8.5 w satsodium bicarbonate solution) for 6 days. The water was removed byfreezing and lyophilization yielding 1.59 grams white solid. ¹-NMR &³¹P-NMR showed the collected polymer to be ≈41% P monomers, and 59% Smonomers. Analysis of the P containing groups showed ≈22%phosphono-phosphate groups with a small amount ofphosphono-pyrophosphate groups. The remaining P containing groupsappeared to be a mixture of phosphonate and phosphonate anhydridestructures. The polymer was calculated as 87.4% weight active.

Example 51 Co-Polymerization of Vinyl Phosphono-monoPhosphate (VPP) andSodium Vinyl Sulfonate (SYS) with Purification

VPP (made on larger scale as described in Example 1, 64.6 g active, 254mmoles) and SVS (25% aqueous solution, 161.6 g, 310 mmoles), initialmolar ratio of SVS to VPP of 55 to 45, were charged in a 500 mL roundbottom flask, stirred and the headspace of the flask purged with flowingnitrogen for 60 minutes. The pH of the solution was raised from 8.5 to10.5 by addition of 9.5 mL of 1M NaOH. The flask purged with flowingnitrogen and heated to 60° C. at which time Ammonium Persulfate (APS,Aldrich, 7.73 mL of a 10% solution in water, mg, 0.6% relative to totalmonomers) was added. The resultant was stirred 24 hrs at 60° C.

¹H-NMR & ³¹P-NMR were run on the crude reaction solutions. Total monomerconversion of 78% was observed with broad P polymer peaks at ˜18 to 23ppm from the phosphonate group and -6 to −10 from the phosphate bound tothe phosphonate group.

The polymer was purified by adding methanol aliquots over 15 minutes toa stirred solution containing 10% active polymer. A turbid solutionresulted and was transferred to a separatory funnel and allowed to standfor an additional 15 minutes to fully separate into a lower viscouspolymer rich syrup and an upper fluid layer. The lower polymer layer wascollected and the upper layer reprecipitated using an additional aliquotof methanol and following repeating the same procedure. All samples werethen dried under vacuum for two days with the final mass recorded in theTable 4 below.

TABLE 4 ml Dried Fraction MeOH Mass 1 150 38.6 2 100 11.0 3 50 6.4 4 503.1 5 100 4.2 6 150 4.0

In addition, approximately 50 ml of the remaining upper H₂O/MeOH layerwas concentrated under N₂ stream overnight at room temperature followedby drying for 24 hours under vacuum at room temperature yielding 2.5 gwhite solid. Size exclusion chromatography/gel permeation chromatography(SEC or GPC, 3-columns in series, Polymer Standards Service MCX1000A,MCX500A and MCX100A all 5 μm, with guard column, 0.2M NaNO₃ mobile phase1 mL/min) showed sequential decreases in molecular weight from fraction1 with the highest molecular weight and fraction 6 with the lowest. TheGPC trace plot resulting from the polymer analysis is provided asFIG. 1. Higher molecular weight is represented by a shorter retentiontime, while lower molecular weight has a higher retention time. Thelarge peaks after 22.5 minutes represent non-polymer species such asresidual monomers, and salt impurities in the sodium vinyl sulfatesolution.

Example 52 Additional Purification of Vinyl Phosphono-monoPhosphate(VPP) and Sodium Vinyl Sulfonate (SYS) Samples from Example 51

Additional purification was performed on fractions 1-3 and 4-6. A 15weight % polymer solution in water was created from the combinedfractions 1-3. To this was added a mass of methanol equal to 20% of themass of the entire water fraction of 60 minutes with stirring. Stirringwas stopped and the solution phase separated to give a viscous polymerrich lower layer. This fraction was collected and dried. This procedurewas repeated three additional times with an additional 10% methanolrelative to the starting mass of solution added each time. All sampleswere oven dried with the percent of original mass recorded in the tablebelow. Fractions 1-4 were 77-81% active with less than 0.5% phosphate,less than 0.2% vinyl phosphate or vinyl phosphono-phosphate, with nodetectable vinyl sulfonate.

TABLE 5 % % of Fraction MeOH Total 1 20% 73% 2 30% 14% 3 40% 5% 4 50% 4%Residual 4%

A 20 weight percent polymer solution was created from the combinedfractions 4-6. To this solution was added a mass of methanol equal to60% of the total mass of the solution. The resulting precipitant wasdried under vacuum for two days. The recovered polymer mass was 93% ofthe initial, 83% active, with less than 0.5% phosphate, less than 0.1%vinyl sulfonate, and less than 0.1% vinyl phosphonate or vinylphosphonate.

The GPC trace plot of the resulting refractioned materials is shown inFIG. 2.

In addition to RI detection, light scattering was also performed. Whilethe low retention time samples provide good light scattering, higherretention samples do not. This phenomenon was independently confirmedwith a standalone light scattering instrument not attached to GPC. Lowmolecular weight fractions appear to cluster which manifests as highmolecular weight and high error after work up of light scattering signalinto molecular weight. For this reason, only the molecular weights ofthe less retained materials are given. For more retained fraction, thetrend of increasing calculated Mn and Mw continues with uncertaintiesapproaching 50%. Polymer with Mw of 60,000 Daltons was detected forRefrac 1-3-1. This corresponds to a polymer of between 250 and 450repeat units depending upon the composition of vinyl sulfonate and vinylphosphono-phosphate derived units.

TABLE 6 Mn Mw (kDa) Uncertainty (kDa) Uncertainty Fractions 1-3 4.42.50% 6.5 1.60% Refrac 1-3-1 5.6 1.10% 6.8 0.90% Refrac 1-3-2 3.5 4.30%4.0 3.90% Refrac 1-3-3 4.0 7.50% 4.9 12.30% Refrac 1-3-4 4.6 7.60% 6.118.90%

Example 53 Identification of End Groups by Different AnalyticalTechniques

HNMR of the refractionated samples from example 61 showed broad polymerpeaks in the olefin region of 6.5-5 ppm. Integration of these peaksversus the non-olefin peaks from 4.0-1.0 ppm can be used to approximatehow many olefins are present. Olefin areas were divided by 2 assuming avinyl like group, while the non-olefins were divided by 3 assuming aCH₂—CHX where X is a P or S. From the composition of each fraction,calculated with an internal standard combined HNMR and PNMR, the Mn canbe approximated under the assumption that every olefin corresponds to aterminal group. The closeness of this calculation with the lightscattering (LS) result for Mn can then be used to gauge if each polymerhas an olefin at a terminal position. The comparative results are givenin Table 7.

TABLE 7 Mn-LS MW-LS Mn-HNMR (kDa) (kDa) (kDa) Fractions 1-3 4.4 6.5 3.5Refrac 1-3-1 5.6 6.8 6.8 Refrac 1-3-2 3.5 4 2.7 Refrac 1-3-3 4 4.9 2.3Refrac 1-3-4 4.6 6.1 2.0 Refrac 1-3 - Residual — — 0.8 Fractions 4-6 — —1.3 Refrac 4-6-1 — — 1.4 Refrac 4-6 - Residual — — 1.2

For the less retained and presumably higher molecular weight species,the match is quite close, with values of 5.6 vs 6.8 and 3.5 vs. 2.7 forRefrac 1-3-1 and 2. Unlike light scattering, olefin-based analysis alsoindicates that Mn does decrease with higher fractions that are moreretained on the columns. To confirm the CH₂ nature of the olefins,edited heteronuclear single quantum coherence (Edited-HSQC) NMR was runon sample Refrac 4-6-1. The olefin peaks were confirmed to be of CH₂character.

Sample Refrac 1-3-4 was also analyzed by ion chromatography (DionexIonPac AS 16-4 μm) followed by high resolution mass spectrometry. Inaddition to a large broad polymer peak with many signals, a sharp earlyeluting (less total charge) peak was also seen. This early eluting peakwas found to contain and match the multiple masses for a “trimer” ofphosphono-phosphate, including the proton form, sodium form, mixtures ofproton and sodium as well as masses corresponding to the loss or gain ofwater and loss of a phosphate group. This species was found to containan unsaturation, either olefinic or cyclic. Given the Edited-HSQCresult, the structure of the fully protonic form is shown.

It is assumed that other end groups besides olefins are also present. Inthe synthesis of the refractionated samples, 0.6% initiator relative tototal moles of polymerizable monomers was used. Typical initiatorefficiency is less than 100%, but for the sake of calculation this valuewill be used. Each persulfate can split to form 2 radicals. If eachradical starts a polymer chain and the reaction proceeds to completion,each chain is expected to have 83 repeat units. The initial combinedfraction 1-3 had an average of 19 repeat units while 4-6 had 6 repeatunits from the HNMR data. Therefore, assuming every initiator radicalperfectly initiated a polymer, a minimum of 4 chain transfers or backbiting and beta scission combinations took place on that chain, witheach transfer likely producing an olefin. Assuming only 40% efficiencyof initiation, 208 repeat units is expected meaning 11 chain transfersor back biting and beta scission combinations occurred from eachinitiator radical.

Example 54 Mixtures of VPP/SYS Copolymer with Transition Metal Salts

A 6 wt % polymer solution from Refrac 4-6-1 of Example 52 was created byadding 1.8 g of dried 83% active polymer to 24.7 g of water. Stocksolutions of transition metal salts at 0.15 M were created by adding theappropriate mass of chloride salt of Ca, Cu, Fe(II), Mg, Mn, Ni, Sn, Zn,Fe(III) and Al(III), to a 10 mL volumetric flask, and filling withreverse osmosis (RO) water to the mark. Stock solutions of 0.15 and0.225 M Na₂CO₃, and 0.1 and 0.15 M Na₃PO₄, were likewise made by addingthe appropriate mass to a 25 mL volumetric flask and filling with ROwater to the mark.

Five samples were made for each metal. The first contained the 1 mL of0.15 M metal chloride (MC) and 2 mL of RO water. The second samplecontained 1 mL of 0.15 M metal chloride, 1 mL of RO water and either 1mL of 0.15 M Na₂CO₃ for the divalent metal ions, Ca, Cu, Fe(II), Mg, Mn,Ni, Sn and Zn or 1 mL of 0.225 M Na₂CO₃ for the trivalent metals Fe(III)and Al(III). The third sample contained 1 mL of 0.15M metal chloride,and either 1 mL of 0.1 M Na₃PO₄ for the divalent metal ions, Ca, Cu,Fe(II), Mg, Mn, Ni, Sn and Zn or 1 mL of 0.15 M Na₃PO₄ for the trivalentmetals Fe(III) and Al(III). The fourth sample contained 1 mL of 0.15Mmetal chloride, 1 mL of 6 wt % polymer solution water (denoted POP) andeither 1 mL of 0.15 M Na₂CO₃ for the divalent metal ions, Ca, Cu,Fe(II), Mg, Mn, Ni, Sn and Zn or 1 mL of 0.225 M Na₂CO₃ for thetrivalent metals Fe(III) and Al(III). The last sample contained 1 mL of0.15M metal chloride, 1 mL of 6 wt % polymer solution (denoted POP) andeither 1 mL of 0.1 M Na₃PO₄ for the divalent metal ions, Ca, Cu, Fe(II),Mg, Mn, Ni, Sn and Zn or 1 mL of 0.15 M Na₃PO₄ for the trivalent metalsFe(III) and Al(III). After addition of all components in the ordernoted, each vial was capped and shaken vigorously and allowed to sitovernight. A visible sediment formed for several samples and collectedat the bottom of the vial. 1 mL of solution was carefully pipetted fromeach sample and submitted for analysis by inductively coupled plasmamass spectrometry (ICP-MS). The concentration of each metal ion in unitsof mM in the supernatant is given in Table 5. The total targeted maximumvalue for each metal was approximately 50 mM.

TABLE 5 Ca Cu Fe(II) Mg Mn Ni Sn Zn Fe(III) Al(III) Metal Chloride (MC)51 43 50 49 49 49 35 48 50 51 MC + Na₂CO₃ 1 0.04 3 32 2 5 0.3 3 49 34MC + Na₃PO₄ 0.4 0.1 0.1 0.9 0.4 2 0.1 0.03 13 12 MC + Na₂CO₃ + POP 53 4450 50 51 50 25 49 48 54 MC + Na₃PO₄ + POP 53 41 49 47 51 50 36 24 55 53

Example 55 Mixtures of VPP/SYS and VPA/SYS Copolymers with Calcium

The procedure of example 54 was conducted using a copolymer containingVPP and VSA residues (Example 20, 66% sulfonate, 30%phosphono-phosphate, denoted POP) and a copolymer containing VPA and SVSresidues (Example 17, 56% sulfonate, 44% phosphonate, denoted P/S). Afinal solution of 50 mM Calcium chloride was tested with and withoutthese two polymers at 2 wt %. In addition to Na₂CO₃ and Na₃PO₄, NaF wasalso tested as an anion. The concentration of Ca in units of mM asdetermined by ICP-MS in the supernatant is given in Table 6. The totaltargeted maximum value is 50 mM.

TABLE 6 No Polymer POP P/S 50 mM CaCl2 48 47 47 50 mM CaCl2 + 100 mM NaF0.03 48 45 50 mM CaCl2 + 50 mM Na₂CO₃ 0.03 47 44 50 mM CaCl2 + 33.3 mMNa₃PO₄ 0.01 42 46

Example 56 Mixtures of Phosphono-Phosphate Containing Polymers withMultivalent Cations

An aqueous solution containing polymers described in Examples, 6, 16-40,42, 48, 50 or 51, and a multivalent metal cation is created. When theintroduction of individual anion or mixtures of anions such as F⁻, Cl⁻,Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄ ⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇ ⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and (PO₃⁻¹) at a combination of concentration and/or pH causes precipitation ofsaid multivalent metal cation as a salt, it is found that the additionof said polymers has reduced the total metal precipitated.

Examples 57-60—Scale Up and Testing in Oral Care Formulations

The following examples demonstrate aqueous compositions of the polymerscontaining phosphono-phosphates with multivalent cations wherein saidaqueous composition is a dentifrice.

Example 57-20-30 g Scale Up of Example 19 and 20

The procedure of examples 19 and 20 was scaled up using 96.7 mmoles ofVPP and 96.7 mmoles of VS A with an equivalent increase of otherreagents and solvents. After dialysis and freeze drying, 27.1 g ofpolymer was collected and found to contain 59% monomers based on SVS,40% based on VPP and 2% based on VP A. The polymer was 83% active on aweight basis with 17% impurities/water.

Example 58-20-30 g Scale Up of Example 16 and 17

The procedure of examples 16 and 17 was scaled up using 148 mmoles ofVPP and 122 mmoles of VSA with an equivalent increase of other reagentsand solvents. After dialysis and freeze drying, 26.8 g of polymer wascollected and found to contain 54% monomers based on SVS, 46% based onVP A. The polymer was 90% active on a weight basis with 10%impurities/water.

Example 59-100 g Scale Up of Example 19 and 20

The procedure of examples 19 and 20 was scaled up using 354.5 mmoles ofVPP and 433 mmoles of VSA with an equivalent increase of other reagentsand solvents. After neutralization the bulk solution was brought up to9819 g with water and pH adjusted to 10 with 1N NaOH. Low MW impuritieswere reduced in the resultant solution by Tangential Flow Filtration(TEE) using Tami Industries 1000 MWCO column (E190613N001). The solutionwas pumped from a reservoir through the column and back into thereservoir. The effluent that passed through the pores of the column wascollected in a flask on a balance. In the first run, the solution waspumped until 3.5 kg of effluent was collected. The remaining solution inthe reservoir was then brought back up to around 9 kg. The procedure wasrepeated with 4.8 kg removed and the reservoir brought up to 11 kg. Inthe final run, 6 kg of effluent was removed. After the final TFT theconcentrated solution was filtered thru a 0.22μ m filter (Stericup 500ml Filter Unit, Aldrich).

The water was removed from the final TFF concentrate after filtering byevaporation under flowing nitrogen for 5 days at room temperatureyielding 173 g tan paste. This was further dried under vacuum at >1 Torrfor 48 hours yielding 137.2 g light tan solid. The solid was found tocontain 66% monomers based on SVS, 34% based on VPP. The polymer was 80%active on a weight basis with 20% impurities/water.

Example 60—Formulation and Testing of Examples 57-59

In this example, all percentages are by weight unless otherwise noted.

The compositions were prepared as follows:

Composition #1 was commercially purchased Crest Cavity ProtectionRegular Flavor.

Composition #2 was commercially purchased Crest ProHealth Clean MintSmooth Formula.

Composition #3 is the same as Composition #2 with the addition ofPolymer Example 56.

Composition #2 was weighed into a Speedmix jar. The polymer Example 57was then added to the Speedmix jar and mixed in a Speedmixer untilhomogeneous. The pH was then determined with a pH electrode and 2N HClwas added and mixed in a Speedmixer to adjust the pH to a target of ˜6.

Composition #4 is the same as Composition #2 with the addition ofPolymer Example 58. Composition #2 was weighed into a Speedmix jar. Thepolymer Example 58 was then added to the Speedmix jar and mixed in aSpeedmixer until homogeneous. The pH was then determined with a pHelectrode and 50% NaOH solution was added and mixed in a Speedmixer toadjust the pH to a target of ˜6.

Composition #5 was prepared in a pilot scale mixer by addingapproximately half of the sorbitol to the mixer, heating to 65° C. witha heating/cooling jacket on the tank and pulling vacuum. In a separatecontainer 1 weight percent of the silica and all the hydroxyethylcellulose were dry blended until homogeneous and then drawn by vacuuminto the mixing vessel. A both an anchor agitator and high shearrotor/stator device were used to mix and homogenize the mixture toassure homogeneity and hydration of the hydroxyethyl cellulose. Oncehomogeneous, the rotor/stator device was turned off. The remainingsorbitol, about 25% of the water and all the blue dye were added andmixed until homogeneous using the anchor agitator. In a separatecontainer, 1 weight percent of the silica, all the saccharin and all thecarrageenan were dry blended and drawn into the main mix vessel undervacuum with the high shear rotor/stator device and anchor agitatorrunning. Once homogenous, the rotor/stator was turned off. Next theremaining silica was drawn into the main mix vessel under vacuum andmixed using the achor agitator at a vacuum not less than 26 inches ofmercury. The batch was then cooled to approximately 49° C. via theheating/cooling jacket while continuing to be mixed with the anchoragitator. Once the batch reached 49° C., the achor agitator was stopped,the mixer was opened and the flavor and sodium lauryl sulfate solutionwere added to the top of the batch. Vacuum was then pulled to 24 inchesof mercury and the anchor agitator and rotor/stator were turned on untilthe batch was homogeneously mixed. After mixing, the rotor/stator wasturned off and vacuum was pulled to 27 inches of mercury to remove air.In a separate container, the remaining 75% of the water was heated to 65C. Sodium gluconate was added to the water and mixed until dissolved.Stannous fluoride was then added to the gluconate solution and mixeduntil dissolved. Stannous chloride was then added to the gluconatesolution and mixed until dissolved. Once this solution was prepared, itwas added under vacuum to the main mix vessel and mixed using the anchoragitator until homogeneous. After the mixing, the sodium hydroxide wasadded under vacuum to the main mix vessel and the anchor agitator androtor/stator were used to mix homogeneously. Once homogeneous, therotor/stator was turned off and the heating/cooling jacket was reducedto 30° C. and vacuum was pulled to 26 inches of mercury. The batch wasmixed under vacuum until the temperature reached 35° C., it was pumpedout of the main mix vessel.

Composition #6 is the same as Composition #5 with the addition ofPolymer Example 59. Composition #5 was weighed into a Speedmix jar. Thepolymer Example 59 was then added to the Speedmix jar and mixed in aSpeedmixer until homogeneous. The pH was then determined with a pHelectrode and no further adjustment was needed to achieve a pH of ˜6.

Composition #7 is the same as Composition #2 with the addition ofPolymer Example 59. Composition #2 was weighed into a Speedmix jar. Thepolymer Example 59 was then added to the Speedmix jar and mixed in aSpeedmixer until homogeneous. The pH was then determined with a pHelectrode and 50% NaOH solution was added and mixed in a Speedmixer toadjust the pH to a target of ˜6.

TABLE 7 Composition #5 Composition Formula #2 #1 Composition CompositionComposition Nil Polymer Composition Composition iPTSM #2 #3 #4 (iPTSM #6#7 Negative Formula #1 Formula #1 Formula #1 Positive Formula #2 Formula#1 Control Nil Polymer w/Example 57 w/Example 58 Control) w/Example 59w/Example 59 H2O 11.165 21.156 20.599 20.719 13 12.684 20.492 NaF 0.243SnF2 0.454 0.442 0.445 0.454 0.443 0.44 NaOH (50%) 0.87 0.847 0.881 0.80.781 0.843 Sorbitol 65.508 48 46.737 47.009 55.159 53.819 46.493Monosodium Phosphate 0.419 dihydrate Trisodium Phosphate 1.1Dodecahydrate Carboxy Methyl 0.75 Cellulose Carbomer 956 0.3 Z119 150.056 0.055 0.055 20 19.514 0.054 Z109 17.5 17.039 17.139 0 0 16.951TiO2 0.525 0.5 0.487 0.49 0.25 0.244 0.484 Carrageenan 1.5 1.461 1.4690.8 0.781 1.453 Xanthan Gum 0.875 0.852 0.857 0 0 0.848 HydroxyethylCellulose 0 0.5 0.488 0 Sodium Lauryl Sulfate 4 5.00 4.868 4.897 4 3.9034.843 (29% Sol'n) Saccharin 0.13 0.45 0.438 0.441 0.455 0.444 0.436Flavor 0.81 1.30 1.266 1.273 1 0.976 1.259 ZnCitrate 0.53 0.519 0.522 00 0.516 NaGluconate 1.30 1.266 1.273 2.082 2.031 1.259 SnCl2*2H2O 0.510.492 0.495 1.5 1.464 0.49 2N HCl 0.28 0.277 0 0 0.726 Dye Solution 0.05Example 57 (VSA/VPP) 2.35 2.355 0 0 0 Example 58 (VSA/VPA) 0 0 2.036 0 0Example 59 (VSA/VPP) 0 2.43 2.412 Total 100 100 100 100 100 100 100

Example 61 Additional Mixtures of VPP/SYS Copolymer with TransitionMetal Salts

The procedure of example 54 was followed using a 6 wt % polymer solutionfrom Refrac 4-6-1 of Example 52, created by adding 0.9 g of dried 83%active polymer to 15 g total. Stock solutions of transition metal saltsat 0.15 M were created by adding the appropriate mass of chloride saltof Ca, Sn, and Zn to a 10 mL volumetric flask, and filling with reverseosmosis (RO) water to the mark. Stock solutions of 0.15 M Na₂PO₃F(disodium monofluorophosphate, MFP), 0.075M Na₄P₂O₇ (tetra sodiumpyrophosphate), 0.30 M (NaPO₃) (polyphosphate, concentration ofindividual repeat unit as explained in definitions), and 0.15M Na₂SO₄,were likewise made by adding the appropriate mass to a 10 mL volumetricflask and filling with RO water to the mark.

Nine samples were made for each Ca, while seven were made for Sn and Zn.For all samples, the first contained the 1 mF of 0.15 M metal chloride(MC) and 2 mF of RO water. The second sample contained 1 mF of 0.15 Mmetal chloride, 1 mF of RO water and 1 mL 0.15 M Na₂PO₃F. The thirdsample contained 1 mF of 0.15M metal chloride, 1 mF of RO water and0.075M Na₄P₂O₇. The fourth sample contained 1 mF of 0.15M metalchloride, 1 mL of RO water and 1 mL of 0.30 (NaPO3). The fifth samplecontained 1 mF of 0.15 M metal chloride, 1 mF of 6 wt % polymer solutionwater (denoted POP) and 1 mL 0.15 M Na₂PO₃F. The sixth sample contained1 mF of 0.15M metal chloride, 1 mF of 6 wt % POP and 0.075M Na₄P₂O₇. Theseventh sample contained 1 mF of 0.15M metal chloride, 1 mF of 6 wt %POP and 1 mL of 0.30 (NaPO₃). For Ca, the eighth sample contained 1 mFof 0.15M CaCl₂, 1 mF of RO water, and 1 mF of 0.15 Na₂SO₄. The finalsample for Ca contained 1 mF of 0.15M CaCl₂, 1 mF of 6 wt % POP, and 1mF of 0.15 Na₂SO₄.

After addition of all components in the order noted above, each vial wascapped and shaken vigorously and allowed to sit overnight. A visiblesediment formed for several samples and collected at the bottom of thevial. 1 mL of solution was carefully pipetted from each sample andsubmitted for analysis by inductively coupled plasma mass spectrometry(ICP-MS). An unsettled suspension formed for samples with Ca andpyrophosphate, and Ca, pyrophosphate and polymer. This suspension wasmeasured directly in ICP and passed through a 45 μm filter and measuredon ICP. The concentration of each metal ion in units of mM in thesupernatant is given in Table 8. The total targeted maximum value foreach metal was approximately 50 mM.

TABLE 8 Ca Sn Zn Metal Chloride (MC) 52 43 43 MC + Na₂PO₃F 47 9.0 40MC + Na₄P₂O₇ 53 6.2 <0.3 MC + (NaPO₃) 35 12 42 MC + Na₂PO₃F + POP 52 5040 MC + Na₄P2O₇ + POP 51 51 42 MC + (NaPO₃) + POP 53 51 39 MC + Na₂SO₄53 — — MC + Na₂SO₄ + POP 52 — — MC + Na₄P₂O₇ Filtered 2.6 — — MC +Na₄P₂O₇ + POP Filtered 29 — —

It is understood that the examples and embodiments described herein arefor illustrative purposes only and that various modifications or changesin light thereof will be suggested to one skilled in the art withoutdeparting from its spirit and scope.

What is claimed is:
 1. An aqueous composition comprising a metal saltcomprising one or more multivalent cations and a polymer having thestructure of Formula 1:

wherein: ε is the site of attachment to a carbon atom in the polymerbackbone, side group, or side chain; R₁ is selected from the groupconsisting of —H, metal salt having Na, K, or L₁ cation, amine cationsalt, and a structure of Formula 2:

wherein: θ is the site of attachment to Formula 1, R₄ and R₅ areindependently selected from the group consisting of —H, metal salthaving Na, K, or L₁ cation, and amine cation salt; R₂ is selected fromthe group consisting of —H, metal salt having Na, K, or L₁ cation, aminecation salt, and a structure of Formula 3:

wherein: θ is the site of attachment to Formula 1, R₆, and R₇ areindependently selected from the group consisting of —H, metal salthaving Na, K, or L₁ cation, and amine cation salt, and n is an integerfrom 1 to 22; and R₃ is selected from the group consisting of —H, metalsalt having Na, K, or L₁ cation, and amine cation salt.
 2. Thecomposition of claim 1 wherein the multivalent metal cations areselected from the group consisting of Ca, Cu, Ni, Mg, Mn, Sn, Zn, Fe,and Al.
 3. The composition of claim 1 wherein the aqueous compositionfurther comprises an anion selected from the group consisting of F⁻,Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄ ⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻²,HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇ ⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and(PO₃ ⁻¹).
 4. The composition of claim 1 further comprising an additionalmetal salt having a monovalent cation.
 5. The composition of claim 2wherein the aqueous composition further comprises an anion selected fromthe group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹).
 6. The composition of claim 5wherein the aqueous composition further comprises an additional metalsalt having a monovalent cation.
 7. The composition of claim 1 whereinsaid polymer further comprises a repeat unit with a structure of Formula4:

wherein: ω is the site of attachment to the phosphono-phosphate group ofFormula 1; ψ are the sites of attachment to other repeat units in thepolymer backbone; R₈ is selected from the group consisting of —H and—CH₃; L₁ is selected from the group consisting of a chemical bond,arenediyl, and a structure of Formula 4:

wherein: α is the site of attachment to the polymer backbone; β is thesite of attachment to the phosphono-phosphate group of Formula 1; X isselected from the group consisting of the structures in Formulas6-Formula 6

wherein: R₉ is selected from the group consisting of —H, alkyl_((C1-8)),phosphonoalkyl, and phosphono(phosphate)alkyl; and Y is selected fromthe group consisting of alkanediyl, alkoxydiyl, alkylaminodiyl andalkenediyl.
 8. The composition of claim 7 wherein the multivalent metalcations are selected from the group consisting of Ca, Cu, Ni, Mg, Mn,Sn, Zn, Fe, and Al.
 9. The composition of claim 7 wherein the aqueouscomposition further comprises an anion selected from the groupconsisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄ ⁻³, HPO₄ ⁻²,H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇ ⁻³, H₂P₂O₇ ⁻²,H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹).
 10. The composition of claim 7 furthercomprising an additional metal salt having a monovalent cation.
 11. Thecomposition of claim 8 wherein the aqueous composition further comprisesan anion selected from the group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻²,CO₃ ⁻², HCO₃ ⁻, PO₄ ⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻²,HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇ ³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹).
 12. Thecomposition of claim 11 wherein the aqueous composition furthercomprises an additional metal salt having a monovalent cation.
 13. Amethod of inhibiting at least 10% precipitation of transition metalcomplexes which would otherwise be insoluble in an aqueous mixture fromsolutions by combining said solutions with a polymer comprising thestructure of Formula 1:

wherein: ε is the site of attachment to a carbon atom in the polymerbackbone, side group, or side chain; R₁ is selected from the groupconsisting of —H, metal salt having Na, K, or L₁ cation, amine cationsalt, and a structure of Formula 2:

wherein: θ is the site of attachment to Formula 1, R₄ and R₅ areindependently selected from the group consisting of —H, metal salthaving Na, K, or L₁ cation, and amine cation salt; R₂ is selected fromthe group consisting of —H, metal salt having Na, K, or Li cation, aminecation salt, and a structure of Formula 3:

wherein: θ is the site of attachment to Formula 1, R₆, and R₇ areindependently selected from the group consisting of —H, metal salthaving Na, K, or L₁ cation, and amine cation salt, and n is an integerfrom 1 to 22; and R₃ is selected from the group consisting of —H, metalsalt having Na, K, or Li cation, and amine cation salt.
 14. The methodof claim 13 wherein said polymer further comprises a repeat unit with astructure of Formula 4:

wherein: ω is the site of attachment to the phosphono-phosphate group ofFormula 1; ψ are the sites of attachment to other repeat units in thepolymer backbone; R₈ is selected from the group consisting of —H and—CH₃; L₁ is selected from the group consisting of a chemical bond,arenediyl, and a structure of Formula 4:

wherein: α is the site of attachment to the alkenyl radical; β is thesite of attachment to the phosphono-phosphate group of Formula 1; X isselected from the group consisting of the structures in Formulas6-Formula 6

wherein: R₉ is selected from the group consisting of —H, alkyl_((C1-8)),phosphonoalkyl, and phosphono(phosphate)alkyl; and Y is selected fromthe group consisting of alkanediyl, alkoxydiyl, alkylaminodiyl andalkenediyl.
 15. The method of claim 13 wherein the transition metalcomplexes which would otherwise be insoluble comprises one or moremultivalent metal cations selected from the group consisting of Ca, Cu,Ni, Mg, Mn, Sn, Zn, Fe, and Al.
 16. The method of claim 13 wherein thetransition metal complexes which would otherwise be insoluble comprisesone or more anions selected from the group consisting of F⁻, Cl⁻, Br⁻,I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄ ⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻,PO₃F⁻², HPO₃F⁴, P₂O₇ ⁻⁴, HP₂O₇ ⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹).17. The method of claim 13 wherein the aqueous mixture comprises a metalsalt having a monovalent cation.
 18. The method of claim 15 wherein thetransition metal complexes which would otherwise be insoluble comprisesone or more anions selected from the group consisting of F⁻, Cl⁻, Br⁻,I⁻, OH⁻S⁻², CO₃ ⁻², HCO₃ ⁻, PO₄ ⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻,PO₃F⁻², HPO₃F⁻¹, P₂O₇ ⁻⁴, HP₂O₇ ⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹).19. The method of claim 18 wherein the aqueous mixture comprises a metalsalt having a monovalent cation.
 20. A method of making a stable aqueousmetal salt composition, said method comprising the steps of: dissolvinga metal salt comprising one or more multivalent cations in an aqueoussolution comprising water to form an aqueous metal salt composition; andadding to said aqueous metal salt composition a polymer comprising thestructure of Formula 1:

wherein: ε is the site of attachment to a carbon atom in the polymerbackbone, side group, or side chain; R₁ is selected from the groupconsisting of —H, metal salt having Na, K, or L₁ cation, amine cationsalt, and a structure of Formula 2:

wherein: θ is the site of attachment to Formula 1, R₄ and R₅ areindependently selected from the group consisting of —H, metal salthaving Na, K, or L₁ cation, and amine cation salt; R₂ is selected fromthe group consisting of —H, metal salt having Na, K, or Li cation, aminecation salt, and a structure of Formula 3:

wherein: θ is the site of attachment to Formula 1, R₆, and R₇ areindependently selected from the group consisting of —H, metal salthaving Na, K, or L₁ cation, and amine cation salt, and n is an integerfrom 1 to 22; and R₃ is selected from the group consisting of —H, metalsalt having Na, K, or Li cation, and amine cation salt.
 21. The methodof claim 20 wherein said polymer further comprises a repeat unit with astructure of Formula 4:

wherein: ω is the site of attachment to the phosphono-phosphate group ofFormula 1; ψ are the sites of attachment to other repeat units in thepolymer backbone; R₈ is selected from the group consisting of —H and—CH₃; L₁ is selected from the group consisting of a chemical bond,arenediyl, and a structure of Formula 4:

wherein: α is the site of attachment to the alkenyl radical; β is thesite of attachment to the phosphono-phosphate group of Formula 1; X isselected from the group consisting of the structures in Formulas6-Formula 6

wherein: R₈ is selected from the group consisting of —H, alkyl_((C1-8)),phosphonoalkyl, and phosphono(phosphate)alkyl; and Y is selected fromthe group consisting of alkanediyl, alkoxydiyl, alkylaminodiyl andalkenediyl.
 22. The method of claim 20 wherein the one or moremultivalent metal cations are selected from the group consisting of Ca,Cu, Ni, Mg, Mn, Sn, Zn, Fe, and Al.
 23. The method of claim 20 whereinthe aqueous metal salt composition further comprises one or more anionsselected from the group consisting of F⁻, Cl⁻, Br⁻, I⁻, OH⁻S⁻², CO₃ ⁻²,HCO₃ ⁻, PO₄ ⁻³, HPO₄ ⁻², H₂PO₄ ⁻¹, SO₄ ⁻², HSO₄ ⁻, PO₃F⁻², HPO₃F⁻¹, P₂O₇⁻⁴, HP₂O₇ ⁻³, H₂P₂O₇ ⁻², H₃P₂O₇ ⁻¹, and (PO₃ ⁻¹).
 24. The method ofclaim 20 wherein the aqueous metal salt composition further comprises ametal salt having a monovalent cation.